CONCENTRATION OF Pu USING OXALATE TYPE CARRIER

DOEpatents

Ritter, D.M.; Black, R.P.S.

1960-04-19

A method is given for dissolving and reprecipitating an oxalate carrier precipitate in a carrier precipitation process for separating and recovering plutonium from an aqueous solution. Uranous oxalate, together with plutonium being carried thereby, is dissolved in an aqueous alkaline solution. Suitable alkaline reagents are the carbonates and oxulates of the alkali metals and ammonium. An oxidizing agent selected from hydroxylamine and hydrogen peroxide is then added to the alkaline solution, thereby oxidizing uranium to the hexavalent state. The resulting solution is then acidified and a source of uranous ions provided in the acidified solution, thereby forming a second plutoniumcarrying uranous oxalate precipitate.

Solubility of Plutonium (IV) Oxalate During Americium/Curium Pretreatment

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

Rudisill, T.S.

1999-08-11

Approximately 15,000 L of solution containing isotopes of americium and curium (Am/Cm) will undergo stabilization by vitrification at the Savannah River Site (SRS). Prior to vitrification, an in-tank pretreatment will be used to remove metal impurities from the solution using an oxalate precipitation process. Material balance calculations for this process, based on solubility data in pure nitric acid, predict approximately 80 percent of the plutonium in the solution will be lost to waste. Due to the uncertainty associated with the plutonium losses during processing, solubility experiments were performed to measure the recovery of plutonium during pretreatment and a subsequent precipitationmore » process to prepare a slurry feed for a batch melter. A good estimate of the plutonium content of the glass is required for planning the shipment of the vitrified Am/Cm product to Oak Ridge National Laboratory (ORNL).The plutonium solubility in the oxalate precipitation supernate during pretreatment was 10 mg/mL at 35 degrees C. In two subsequent washes with a 0.25M oxalic acid/0.5M nitric acid solution, the solubility dropped to less than 5 mg/mL. During the precipitation and washing steps, lanthanide fission products in the solution were mostly insoluble. Uranium, and alkali, alkaline earth, and transition metal impurities were soluble as expected. An elemental material balance for plutonium showed that greater than 94 percent of the plutonium was recovered in the dissolved precipitate. The recovery of the lanthanide elements was generally 94 percent or higher except for the more soluble lanthanum. The recovery of soluble metal impurities from the precipitate slurry ranged from 15 to 22 percent. Theoretically, 16 percent of the soluble oxalates should have been present in the dissolved slurry based on the dilution effects and volumes of supernate and wash solutions removed. A trace level material balance showed greater than 97 percent recovery of americium-241 (from the

Oxalate Synthesis and Pyrolysis: A Colorful Introduction to Stoichiometry

ERIC Educational Resources Information Center

Vannatta, Michael W.; Richards-Babb, Michelle; Sweeney, Robert J.

2010-01-01

Metal oxalate synthesis and pyrolysis provides an opportunity for students to (i) learn stoichiometry, (ii) experience the consequences of proper stoichiometric calculations and experimental techniques, and (iii) be introduced to the relevance of chemistry by highlighting oxalates in context, for example, usages and health effects. At our…

Determination of thorium and of rare earth elements in cerium earth minerals and ores

USGS Publications Warehouse

Carron, M.K.; Skinner, D.L.; Stevens, R.E.

1955-01-01

The conventional oxalate method for precipitating thorium and the rare earth elements in acid solution exhibits definite solubilities of these elements. The present work was undertaken to establish conditions overcoming these solubilities and to find optimum conditions for precipitating thorium and the rare earth elements as hydroxides and sebacates. The investigations resulted in a reliable procedure applicable to samples in which the cerium group elements predominate. The oxalate precipitations are made from homogeneous solution at pH 2 by adding a prepared solution of anhydrous oxalic acid in methanol instead of the more expensive crystalline methyl oxalate. Calcium is added as a carrier. Quantitative precipitation of thorium and the rare earth elements is ascertained by further small additions of calcium to the supernatant liquid, until the added calcium precipitates as oxalate within 2 minutes. Calcium is removed by precipitating the hydroxides of thorium and rare earths at room temperature by adding ammonium hydroxide to pH > 10. Thorium is separated as the sebacate at pH 2.5, and the rare earths are precipitated with ammonium sebacate at pH 9. Maximum errors for combined weights of thorium and rare earth oxides on synthetic mixtures are ??0.6 mg. Maximum error for separated thoria is ??0.5 mg.

Rare Earth Metals: Resourcefulness and Recovery

NASA Astrophysics Data System (ADS)

Wang, Shijie

2013-10-01

When we appreciate the digital revolution carried over from the twentieth century with mobile communication and the Internet, and when we enjoy our high-tech lifestyle filled with iDevices, hybrid cars, wind turbines, and solar cells in this new century, we should also appreciate that all of these advanced products depend on rare earth metals to function. Although there are only 136,000 tons of annual worldwide demand, (Cho, Rare Earth Metals, Will We Have Enough?)1 rare earth metals are becoming such hot commodities on international markets, due to not only to their increasing uses, including in most critical military hardware, but also to Chinese growth, which accounts for 95% of global rare earth metal production. Hence, the 2013 technical calendar topic, planned by the TMS/Hydrometallurgy and Electrometallurgy Committee, is particularly relevant, with four articles (including this commentary) contributed to the JOM October Issue discussing rare earth metals' resourcefulness and recovery.

Oxalate absorption and endogenous oxalate synthesis from ascorbate in calcium oxalate stone formers and non-stone formers.

PubMed

Chai, Weiwen; Liebman, Michael; Kynast-Gales, Susan; Massey, Linda

2004-12-01

Increased rates of either oxalate absorption or endogenous oxalate synthesis can contribute to hyperoxaluria, a primary risk factor for the formation of calcium oxalate-containing kidney stones. This study involves a comparative assessment of oxalate absorption and endogenous oxalate synthesis in subpopulations of stone formers (SFs) and non-stone formers (NSFs) and an assessment of the effect of ascorbate supplementation on oxalate absorption and endogenous oxalate synthesis. Twenty-nine individuals with a history of calcium oxalate kidney stones (19 men, 10 women) and 19 age-matched NSFs (8 men, 11 women) participated in two 6-day controlled feeding experimental periods: ascorbate-supplement (2 g/d) and no-supplement treatments. An oxalate load consisting of 118 mg of unlabeled oxalate and 18 mg of 13C2 -oxalic acid was administered the morning of day 6 of each experimental period. Mean 13C2 -oxalic acid absorption averaged across the ascorbate and no-supplement treatments was significantly greater in SFs (9.9%) than NSFs (8.0%). SFs also had significantly greater 24-hour post-oxalate load urinary total oxalate and endogenous oxalate levels with both treatments. Twenty-four-hour urinary total oxalate level correlated strongly with both 13C2 -oxalic acid absorption (SFs, r = 0.76; P < 0.01; NSFs, r = 0.62; P < 0.01) and endogenous oxalate synthesis (SFs, r = 0.95; P < 0.01; NSFs, r = 0.92; P < 0.01). SFs are characterized by greater rates of both oxalate absorption and endogenous oxalate synthesis, and both these factors contribute to the hyperoxaluric state. The finding that ascorbate supplementation increased urinary total and endogenous oxalate levels suggested that this practice is a risk factor for individuals predisposed to kidney stones.

Role of cellular oxalate in oxalate clearance of patients with calcium oxalate monohydrate stone formation and normal controls.

PubMed

Oehlschläger, Sven; Fuessel, Susanne; Meye, Axel; Herrmann, Jana; Froehner, Michael; Albrecht, Steffen; Wirth, Manfred P

2009-03-01

To examine the cellular, plasma, and urinary oxalate and erythrocyte oxalate flux in patients with calcium oxalate monohydrate (COM) stone formation vs normal controls. Pathologic oxalate clearance in humans is mostly integrated in calcium oxalate stone formation. An underlying cause of deficient oxalate clearance could be defective transmembrane oxalate transport, which, in many tissues, is regulated by an anion exchanger (SLC26). We studied 2 groups: 40 normal controls and 41 patients with COM stone formation. Red blood cells were divided for cellular oxalate measurement and for resuspension in a buffered solution (pH 7.40); 0.1 mmol/L oxalate was added. The supernatant was measured for oxalate immediately and 1 hour after incubation. The plasma and urinary oxalate were analyzed in parallel. The mean cellular oxalate concentrations were significantly greater in the normal controls (5.25 +/- 0.47 micromol/L) than in those with COM stone formation (2.36 +/- 0.28 micromol/L; P < .01). The mean urinary oxalate concentrations were significantly greater in those with COM stone formation (0.31 +/- 0.02 mmol/L) than in the controls (0.24 +/- 0.02 mmol/L; P < .01). The cellular oxalate concentrations correlated significantly with the plasma (r = 0.49-0.63; P < .01) and urinary oxalate (r = -0.29-0.41; P < .03) concentrations in both groups. The plasma oxalate concentrations correlated significantly with the urinary oxalate concentrations (r = -0.30; P < .03) in the controls and with the erythrocyte oxalate flux (r = 0.25; P < .05) in those with COM stone formation. Our data implicate the presence of a cellular oxalate buffer to stabilize plasma and urinary oxalate concentrations in normal controls.

The oxalate-carbonate pathway: at the interface between biology and geology

NASA Astrophysics Data System (ADS)

Junier, P.; Cailleau, G.; Martin, G.; Guggiari, M.; Bravo, D.; Clerc, M.; Aragno, M.; Job, D.; Verrecchia, E.

2012-04-01

The formation of calcite in otherwise carbonate-free acidic soils through the biological degradation of oxalate is a mechanism termed oxalate-carbonate pathway. This pathway lies at the interface between biological and geological systems and constitutes an important, although underestimated, soil mineral carbon sink. In this case, atmospheric CO2 is fixed by the photosynthetic activity of oxalogenic plants, which is partly destined to the production of oxalate used for the chelation of metals, and particularly, calcium. Fungi are also able to produce oxalate to cope with elevated concentrations of metals. In spite of its abundance as a substrate, oxalate is a very stable organic anion that can be metabolized only by a group of bacteria that use it as carbon and energy sources. These bacteria close the biological cycle by degrading calcium oxalate, releasing Ca2+ and inducing a change in local soil pH. If parameters are favourable, the geological part of the pathway begins, because this change in pH will indirectly lead to the precipitation of secondary calcium carbonate (calcite) in unexpected geological conditions. Due to the initial acidic soil conditions, and the absence of geological carbonate in the basement, it is unexpected to find C in the form of calcite. The activity of the oxalate-carbonate pathway has now been demonstrated in several places around the world, suggesting that its importance can be even greater than expected. In addition, new roles for each of the biological players of the pathway have been revealed recently forcing us to reconsider a global biogeochemical model for oxalate cycling.

Estimation of the oxalate content of foods and daily oxalate intake

NASA Technical Reports Server (NTRS)

Holmes, R. P.; Kennedy, M.

2000-01-01

BACKGROUND: The amount of oxalate ingested may be an important risk factor in the development of idiopathic calcium oxalate nephrolithiasis. Reliable food tables listing the oxalate content of foods are currently not available. The aim of this research was to develop an accurate and reliable method to measure the food content of oxalate. METHODS: Capillary electrophoresis (CE) and ion chromatography (IC) were compared as direct techniques for the estimation of the oxalate content of foods. Foods were thoroughly homogenized in acid, heat extracted, and clarified by centrifugation and filtration before dilution in water for analysis. Five individuals consuming self-selected diets maintained food records for three days to determine their mean daily oxalate intakes. RESULTS: Both techniques were capable of adequately measuring the oxalate in foods with a significant oxalate content. With foods of very low oxalate content (<1.8 mg/100 g), IC was more reliable than CE. The mean daily intake of oxalate by the five individuals tested was 152 +/- 83 mg, ranging from 44 to 352 mg/day. CONCLUSIONS: CE appears to be the method of choice over IC for estimating the oxalate content of foods with a medium (>10 mg/100 g) to high oxalate content due to a faster analysis time and lower running costs, whereas IC may be better suited for the analysis of foods with a low oxalate content. Accurate estimates of the oxalate content of foods should permit the role of dietary oxalate in urinary oxalate excretion and stone formation to be clarified. Other factors, apart from the amount of oxalate ingested, appear to exert a major influence over the amount of oxalate excreted in the urine.

SEPARATION OF TRANSURANIC ELEMENTS FROM RARE EARTH COMPOUNDS

DOEpatents

Kohman, T.P.

1961-11-21

A process of separating neptunium and plutonium values from rare earths and alkaline earth fission products present on a solid mixed actinide carrier (Th or U(IV) oxalate or fluoride) --fission product carrier (LaF/sub 3/, CeF/sub 3/, SrF/sub 2/, CaF/sub 2/, YF/sub 3/, La oxalate, cerous oxalate, Sr oxalate, Ca oxalate or Y oxalate) by extraction of the actinides at elevated temperature with a solution of ammonium fluoride and/or ammonium oxalate is described. Separation of the fission-product-containing carriers from the actinide solution formed and precipitation of the neptunium and plutonium from the solution with mineral acid are also accomplished. (AEC)

Plasma oxalic acid and calcium levels in oxalate poisoning

PubMed Central

Zarembski, P. M.; Hodgkinson, A.

1967-01-01

Observations are reported on five cases of suicide or attempted suicide by poisoning with oxalic acid or ethylene glycol. Elevated oxalic acid levels were observed in the plasma, stomach contents, and a number of tissues. Raised oxalic acid levels in plasma were associated with reduced total and ultrafilterable calcium levels. It is suggested that the reduction in plasma total calcium level is due mainly to the deposition of calcium oxalate in the soft tissues, but inhibition of the parathyroid glands may be a contributory factor. Microscopic examination of various tissues indicated that oxalic acid is deposited in the tissues in two forms: (1) crystalline calcium oxalate dihydrate in the kidney and (2) a non-crystalline complex of calcium oxalate and lipid in liver and other tissues. PMID:5602563

Degradation of oxalate in rats implanted with immobilized oxalate oxidase.

PubMed

Raghavan, K G; Tarachand, U

1986-01-20

Accumulation of oxalate leads to hyperoxaluria and calcium oxalate nephrolithiasis in man. Since oxalate is a metabolic end product in mammals, the feasibility of its enzymic degradation has been tested in vivo in rats by administering exogenous oxalate oxidase. Oxalate oxidase, isolated from banana fruit peels, in its native form was found to be non-active at the physiological pH of the recipient animal. However, its functional viability in the recipient animal was ensured by its prior binding with ethylenemaleic anhydride, thus shifting its pH activity curve towards the alkaline range. Rats implanted with dialysis membrane capsules containing such immobilized oxalate oxidase in their peritoneal cavities effectively metabolized intraperitoneally injected [14C]oxalate as well as its precursor [14C]glyoxalate. The implantation of capsules containing coentrapped multienzyme preparations of oxalate oxidase, catalase and peroxidase led to a further degradation of administered [14C]oxalate in rats.

Plutonium oxalate precipitation for trace elemental determination in plutonium materials

DOE PAGES

Xu, Ning; Gallimore, David; Lujan, Elmer; ...

2015-05-26

In this study, an analytical chemistry method has been developed that removes the plutonium (Pu) matrix from the dissolved Pu metal or oxide solution prior to the determination of trace impurities that are present in the metal or oxide. In this study, a Pu oxalate approach was employed to separate Pu from trace impurities. After Pu(III) was precipitated with oxalic acid and separated by centrifugation, trace elemental constituents in the supernatant were analyzed by inductively coupled plasma-optical emission spectroscopy with minimized spectral interferences from the sample matrix.

Oxalate and Sucralose Absorption in Idiopathic Calcium Oxalate Stone Formers

PubMed Central

Knight, John; Jiang, Juquan; Wood, Kyle D.; Holmes, Ross P.; Assimos, Dean G.

2011-01-01

Objectives Oxalate has been hypothesized to undergo absorption in the large and small intestine by both paracellular and transepithelial transport. Sucralose is a chlorinated sugar that is absorbed by paracellular mechanisms. This study's objective was to better understand intestinal oxalate transport by correlating oxalate and sucralose absorption in idiopathic calcium oxalate stone formers. Methods Idiopathic calcium oxalate stone formers were recruited to provide urine specimens on both a self-selected diet and following a meal containing 90 mg of 13C2-oxalate and 5 grams of sucralose, and a stool sample for determination of Oxalobacter formigenes colonization. The 24 hour urine collections were fractionated into the first 6 hours and the subsequent 18 hours. Sucralose and oxalate excretion were measured during these periods and used to estimate absorption. Results A total of 38 subjects were evaluated. The majority of both the 13C2-oxalate and sucralose absorption occurred within the 0-6 hour collection. The 13C2-oxalate and sucralose absorptions were significantly correlated at the 0-6 hour, the 6-24 hour, and the total 24 hour time periods (p<0.04). All five oxalate hyperabsorbers(> 15% absorption) also absorbed significantly more sucralose during the 0-6 hour and whole 24 hour time points (p<0.04). Oxalobacter formigenes colonization did not significantly alter oxalate absorption. Conclusion The results suggest that the majority of oxalate is absorbed in the proximal portion of the gastrointestinal tract and that paracelluar transport is involved. Augmented paracellular transport, as evidenced by increased sucralose absorption, may also influence oxalate absorption. PMID:21676449

Production of battery grade materials via an oxalate method

DOEpatents

Belharouak, Ilias; Amine, Khalil

2016-05-17

An active electrode material for electrochemical devices such as lithium ion batteries includes a lithium transition metal oxide which is free of sodium and sulfur contaminants. The lithium transition metal oxide is prepared by calcining a mixture of a lithium precursor and a transition metal oxalate. Electrochemical devices use such active electrodes.

Production of battery grade materials via an oxalate method

DOEpatents

Belharouak, Ilias; Amine, Khalil

2014-04-29

An active electrode material for electrochemical devices such as lithium ion batteries includes a lithium transition metal oxide which is free of sodium and sulfur contaminants. The lithium transition metal oxide is prepared by calcining a mixture of a lithium precursor and a transition metal oxalate. Electrochemical devices use such active electrodes.

Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite.

PubMed

Flynn, Elaine D; Catalano, Jeffrey G

2018-06-05

During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. The present study thus explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.

The Roles and Mechanisms of Intestinal Oxalate Transport in Oxalate Homeostasis

PubMed Central

Hatch, Marguerite; Freel, Robert W.

2008-01-01

The mammalian intestine has an important role in the dynamics of oxalate exchange and thereby is significant in the etiology of calcium oxalate nephrolithiasis. Here we review some of the phenomenological observations that have led to the conclusion that anion exchangers (antiporters) are important mediators of secondarily active, net oxalate transport along the intestine (both absorptive and secretory). Understanding the mechanisms of transepithelial oxalate transport has been radically advanced in recent years by the identification of the SLC26 family of anion transporters which has facilitated the identification of specific proteins mediating individual apical or basolateral oxalate transport pathways. Moreover, identification of specific exchangers has underscored their relative importance to oxalate homeostasis as revealed by using knockout mouse models and facilitated studies of oxalate transport regulation in heterologous expression systems. Finally, the significance of oxalate degrading bacteria to oxalate homeostasis is considered from basic and applied perspectives. PMID:18359395

Effect of metal complex formation on the potential of organic aerosols as cloud condensation nuclei

NASA Astrophysics Data System (ADS)

Furukawa, T.; Takahashi, Y.

2010-12-01

Secondary organic aerosols (SOA) play a key role on the solar radiation balance in troposphere, since SOA can act as cloud condensation nuclei (CCN) due to its high hygroscopic nature. Oxalic acid is one of the most dominant components of SOA, which has cooling effects of the earth by acting as CCN. However, it is uncertain whether the oxalic acid can exist as free oxalic acid or metal-oxalate complexes in aerosols, even if there is a largedifference in their solubilities into water. Consequently, XAFS measurement was conducted to demonstrate the presence of metal-oxalate complexes. Size fractionated aerosol samples were collected in Tsukuba (located at northeast about 60 km from Tokyo) using a low-volume Andersen-type air sampler. The sampler had eight stages and a back-up filter. The sampling was conducted during winter and summer in 2002. Calcium oxalate was observed in finer particles in each period from Ca K-edge XANES, and its fractions among total Ca were approximately 20%. Similarly,, Zn oxalate was also detected in finer particles from Zn K-edge XANES and EXAFS. The [Zn-oxalate] / [Zn]total ratio in each period clearly increased with the decrease in the particle diameter. This result revealed that Zn-oxalate was formed in the aqueous phase at particle surfaces or in cloud processing. In other words, Zn-oxalate was abundant at the particle surface, resulting from the increase in the [surface]/[bulk] ratio with decreasing particle size. Based on (i) total concentrations of oxalate, Ca, and Zn determined by ion-chromatography and ICP-AES analyses and (ii) Ca- and Zn- oxalate fractions obtained by XAFS, we determined the fraction of metal-oxalate complexes among total oxalate in aerosols. In winter, Ca- and Zn- oxalate fractions reached about 60% of total oxalate in the ranges of 1.1-2.1 μm and 0.65-1.1 μm, while the value was about 60-80% in the same particle size range in summer. On the other hand, Ca- and Zn- oxalates are highly insoluble, showing that

Origin of Urinary Oxalate

NASA Astrophysics Data System (ADS)

Holmes, Ross P.; Knight, John; Assimos, Dean G.

2007-04-01

Urinary oxalate is mostly derived from the absorption of ingested oxalate and endogenous synthesis. The breakdown of vitamin C may also contribute small amounts to the urinary oxalate pool. The amount of oxalate absorbed is influenced by the oxalate content of the diet, the concentrations of divalent cations in the gut, the presence of oxalate-degrading organisms, transport characteristics of the intestinal epithelium, and other factors associated with the intestinal environment. Knowledge of pathways associated with endogenous oxalate synthesis is limited. Urinary oxalate excretion can be modified using strategies that limit dietary oxalate absorption and the ingestion of oxalogenic substrates such as hydroxyproline.

Near-Earth asteroids: Metals occurrence, extraction, and fabrication

NASA Astrophysics Data System (ADS)

Westfall, Richard

Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

Near-Earth asteroids: Metals occurrence, extraction, and fabrication

NASA Technical Reports Server (NTRS)

Westfall, Richard

1991-01-01

Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

Charge-separated and molecular heterobimetallic rare earth-rare earth and alkaline earth-rare earth aryloxo complexes featuring intramolecular metal-pi-arene interactions.

PubMed

Deacon, Glen B; Junk, Peter C; Moxey, Graeme J; Ruhlandt-Senge, Karin; St Prix, Courtney; Zuniga, Maria F

2009-01-01

Treatment of a rare earth metal (Ln) and a potential divalent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the divalent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.

Polyfunctional inorganic-organic hybrid materials: an unusual kind of NLO active layered mixed metal oxalates with tunable magnetic properties and very large second harmonic generation.

PubMed

Cariati, Elena; Macchi, Roberto; Roberto, Dominique; Ugo, Renato; Galli, Simona; Casati, Nicola; Macchi, Piero; Sironi, Angelo; Bogani, Lapo; Caneschi, Andrea; Gatteschi, Dante

2007-08-01

Mixed M(II)/M(III) metal oxalates, as "stripes" connected through strong hydrogen bonding by para-dimethylaminobenzaldeide (DAMBA) and water, form an organic-inorganic 2D network that enables segregation in layers of the cationic organic NLO-phore trans-4-(4-dimethylaminostyryl)-1-methylpyridinium, [DAMS+]. The crystalline hybrid materials obtained have the general formula [DAMS]4[M2M'(C2O4)6].2DAMBA.2H2O (M = Rh, Fe, Cr; M' = Mn, Zn), and their overall three-dimensional packing is non-centrosymmetric and polar, therefore suitable for second harmonic generation (SHG). All the compounds investigated are characterized by an exceptional SHG activity, due both to the large molecular quadratic hyperpolarizability of [DAMS+] and to the efficiency of the crystalline network which organizes [DAMS+] into head-to-tail arranged J-type aggregates. The tunability of the pairs of metal ions allows exploiting also the magnetic functionality of the materials. Examples containing antiferro-, ferro-, and ferri-magnetic interactions (mediated by oxalato bridges) are obtained by coupling proper M(III) ions (Fe, Cr, Rh) with M(II) (Mn, Zn). This shed light on the role of weak next-nearest-neighbor interactions and main nearest-neighbor couplings along "stripes" of mixed M(II)/M(III) metal oxalates of the organic-inorganic 2D network, thus suggesting that these hybrid materials may display isotropic 1D magnetic properties along the mixed M(II)/M(III) metal oxalates "stripes".

Effects of Rare Earth Metals on Steel Microstructures

PubMed Central

Pan, Fei; Zhang, Jian; Chen, Hao-Long; Su, Yen-Hsun; Kuo, Chia-Liang; Su, Yen-Hao; Chen, Shin-Hau; Lin, Kuan-Ju; Hsieh, Ping-Hung; Hwang, Weng-Sing

2016-01-01

Rare earth metals are used in semiconductors, solar cells and catalysts. This review focuses on the background of oxide metallurgy technologies, the chemical and physical properties of rare earth (RE) metals, the background of oxide metallurgy, the functions of RE metals in steelmaking, and the influences of RE metals on steel microstructures. Future prospects for RE metal applications in steelmaking are also presented. PMID:28773545

Rare earth metal-containing ionic liquids

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

Prodius, Denis; Mudring, Anja-Verena

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Rare earth metal-containing ionic liquids

DOE PAGES

Prodius, Denis; Mudring, Anja-Verena

2018-03-07

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Alkali metal and alkali earth metal gadolinium halide scintillators

DOEpatents

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

2016-08-02

The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

Lowering urinary oxalate excretion to decrease calcium oxalate stone disease

PubMed Central

Knight, John; Assimos, Dean G.

2016-01-01

Dietary modifications should be considered as a first line approach in the treatment of idiopathic calcium oxalate nephrolithiasis. The amounts of oxalate and calcium consumed in the diet are significant factors in the development of the disease due to their impact on urinary oxalate excretion. There are a number of strategies that can be employed to reduce oxalate excretion. The consumption of oxalate-rich foods should be avoided and calcium intake adjusted to 1000–1200 mg/day. To encourage compliance it should be emphasized to patients that they be vigilant with this diet as a deviation in any meal or snack could potentially result in significant stone growth. The evidence underlying these two modifications is outlined and other strategies to reduce urinary oxalate excretion are reviewed. PMID:26614109

Diet, but not oral probiotics, effectively reduces urinary oxalate excretion and calcium oxalate supersaturation.

PubMed

Lieske, John C; Tremaine, William J; De Simone, Claudio; O'Connor, Helen M; Li, Xujian; Bergstralh, Eric J; Goldfarb, David S

2010-12-01

We examined the effect of a controlled diet and two probiotic preparations on urinary oxalate excretion, a risk factor for calcium oxalate kidney stone formation, in patients with mild hyperoxaluria. Patients were randomized to a placebo, a probiotic, or a synbiotic preparation. This tested whether these probiotic preparations can increase oxalate metabolism in the intestine and/or decrease oxalate absorption from the gut. Patients were maintained on a controlled diet to remove the confounding variable of differing oxalate intake from food. Urinary oxalate excretion and calcium oxalate supersaturation on the controlled diet were significantly lower compared with baseline on a free-choice diet. Neither study preparation reduced urinary oxalate excretion nor calcium oxalate supersaturation. Fecal lactobacilli colony counts increased on both preparations, whereas enterococcal and yeast colony counts were increased on the synbiotic. Total urine volume and the excretion of oxalate and calcium were all strong independent determinants of urinary calcium oxalate supersaturation. Hence, dietary oxalate restriction reduced urinary oxalate excretion, but the tested probiotics did not influence urinary oxalate levels in patients on a restricted oxalate diet. However, this study suggests that dietary oxalate restriction is useful for kidney stone prevention.

Crystal growth methods dedicated to low solubility actinide oxalates

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

Tamain, C., E-mail: christelle.tamain@cea.fr; Arab-Chapelet, B.; Rivenet, M.

Two novel crystal growth syntheses dedicated to low solubility actinide-oxalate systems and adapted to glove box handling are described. These methods based on the use of precursors of either actinide metal or oxalic acid have been optimized on lanthanide systems (analogue of actinides(III)) and then assessed on real actinide systems. They allow the synthesis of several actinide oxalate single crystals, Am{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 3}·xH{sub 2}O, Th(C{sub 2}O{sub 4}){sub 2}·6H{sub 2}O, M{sub 2+x}[Pu{sup IV}{sub 2−x}Pu{sup III}{sub x}(C{sub 2}O{sub 4}){sub 5}]·nH{sub 2}O and M{sub 1−x}[Pu{sup III}{sub 1−x}Pu{sup IV}{sub x}(C{sub 2}O{sub 4}){sub 2}·H{sub 2}O]·nH{sub 2}O. It is the first timemore » that these well-known compounds are formed by crystal growth methods, thus enabling direct structural studies on transuranic element systems and acquisition of basic data beyond deductions from isomorphic (or not) lanthanide compounds. Characterizations by X-ray diffraction, UV–visible solid spectroscopy, demonstrate the potentialities of these two crystal growth methods to obtain oxalate compounds. - Graphical abstract: Two new single crystal growth methods dedicated to actinide oxalate compounds. - Highlights: • Use of diester as oxalate precursor for crystal growth of actinide oxalates. • Use of actinide oxide as precursor for crystal growth of actinide oxalates. • Crystal growth of Pu(III) and Am(III) oxalates. • Crystal growth of mixed Pu(III)/Pu(IV) oxalates.« less

Hygroscopic properties of oxalic acid and atmospherically relevant oxalates

NASA Astrophysics Data System (ADS)

Ma, Qingxin; He, Hong; Liu, Chang

2013-04-01

Oxalic acid and oxalates represent an important fraction of atmospheric organic aerosols, however, little knowledge about the hygroscopic behavior of these particles is known. In this study, the hygroscopic behavior of oxalic acid and atmospherically relevant oxalates (H2C2O4, (NH4)2C2O4, CaC2O4, and FeC2O4) were studied by Raman spectrometry and vapor sorption analyzer. Under ambient relative humidity (RH) of 10-90%, oxalic acid and these oxalates hardly deliquesce and exhibit low hygroscopicity, however, transformation between anhydrous and hydrated particles was observed during the humidifying and dehumidifying processes. During the water adsorption process, conversion of anhydrous H2C2O4, (NH4)2C2O4, CaC2O4, and FeC2O4 to their hydrated particles (i.e., H2C2O4·2H2O, (NH4)2C2O4·H2O, CaC2O4·H2O, and FeC2O4·2H2O) occurred at about 20% RH, 55% RH, 10% RH, and 75% RH, respectively. Uptake of water on hydrated Ca-oxalate and Fe-oxalate particles can be described by a multilayer adsorption isotherm. During the dehumidifying process, dehydration of H2C2O4·2H2O and (NH4)2C2O4·H2O occurred at 5% RH while CaC2O4·H2O and FeC2O4·2H2O did not undergo dehydration. These results implied that hydrated particles represent the most stable state of oxalic acid and oxalates in the atmosphere. In addition, the assignments of Raman shift bands in the range of 1610-1650 cm-1 were discussed according to the hygroscopic behavior measurement results.

Literature review for oxalate oxidation processes and plutonium oxalate solubility

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

Nash, C. A.

2015-10-01

A literature review of oxalate oxidation processes finds that manganese(II)-catalyzed nitric acid oxidation of oxalate in precipitate filtrate is a viable and well-documented process. The process has been operated on the large scale at Savannah River in the past, including oxidation of 20 tons of oxalic acid in F-Canyon. Research data under a variety of conditions show the process to be robust. This process is recommended for oxalate destruction in H-Canyon in the upcoming program to produce feed for the MOX facility. Prevention of plutonium oxalate precipitation in filtrate can be achieved by concentrated nitric acid/ferric nitrate sequestration of oxalate.more » Organic complexants do not appear practical to sequester plutonium. Testing is proposed to confirm the literature and calculation findings of this review at projected operating conditions for the upcoming campaign.« less

Water as an agent for the morphology modification of metal oxalate materials on the nanoscale: from sheets to rods

PubMed Central

Kim, Minog; Kim, YooJin; Kwon, WonJong; Yoon, Sungho

2016-01-01

A number of approaches have been used to control the shape of metal oxalates, which often used as precursors for metal oxide nanomaterials. However, attempts to use water as a regulator have not been reported. Here in we report systematic studies on related topics: nanosheets, composed of 1-dimensional [M(C2O4)(EG)] (M = Zn or Co) polymeric structure, could be transformed into nanorods by using water as a shape-shifting agent because water can readily substitute EG ligand, leading alternation of inter-chain hydrogen bonding interactions. In addition, heat-treatment of these nanomaterials with diverse morphologies resulted in porous metal oxides with high degrees of shape retention. PMID:26763973

Hydrothermal growth of cross-linked hyperbranched copper dendrites using copper oxalate complex

NASA Astrophysics Data System (ADS)

Truong, Quang Duc; Kakihana, Masato

2012-06-01

A facile and surfactant-free approach has been developed for the synthesis of cross-linked hyperbranched copper dendrites using copper oxalate complex as a precursor and oxalic acid as a reducing and structure-directing agent. The synthesized particles are composed of highly branched nanostructures with unusual cross-linked hierarchical networks. The formation of copper dendrites can be explained in view of both diffusion control and aggregation-based growth model accompanied by the chelation-assisted assembly. Oxalic acid was found to play dual roles as reducing and structure-directing agent based on the investigation results. The understanding on the crystal growth and the roles of oxalic acid provides clear insight into the formation mechanism of hyperbranched metal dendrites.

An antagonist treatment in combination with tracer experiments revealed isocitrate pathway dominant to oxalate biosynthesis in Rumex obtusifolius L

USDA-ARS?s Scientific Manuscript database

Oxalate accumulates in leaves of certain plants such as Rumex species (Polygonaceae). Oxalate plays important roles in defense to predator, detoxification of metallic ions, and in hydroxyl peroxide formation upon wounding/senescence. However, biosynthetic pathways of soluble oxalate are largely unkn...

Further Studies on Oxalic Acid Biosynthesis in Oxalate-accumulating Plants 1

PubMed Central

Nuss, Richard F.; Loewus, Frank A.

1978-01-01

l-Ascorbic acid functions as a precursor of oxalic acid in several oxalate-accumulating plants. The present study extends this observation to include Rumex crispus L. (curly dock), Amaranthus retroflexus L. (red root pigweed), Chenopodium album L. (lamb's-quarters), Beta vulgaris L. (sugar beet), Halogeton glomeratus M. Bieb. (halogeton), and Rheum rhabarbarum L. (rhubarb). Several species with low oxalate content are also examined. When l-[1-14C]ascorbic acid is supplied to young seedlings of R. crispus or H. glomeratus, a major portion of the 14C is released over a 24-hour period as 14CO2 and only a small portion is recovered as [14C]oxalate, unlike cuttings from 2- or 4-month-old plants which retain a large part of the 14C as [14C]oxalic acid and release very little 14CO2. Support for an intermediate role of oxalate in the release of 14CO2 from l-[1-14C]ascorbic acid is seen in the rapid release of 14CO2 by R. crispus and H. glomeratus seedlings labeled with [14C]oxalic acid. The common origin of oxalic acid carbon in the C1 and C2 fragment from l-ascorbic acid is demonstrated by comparison of 14C content of oxalic acid in several oxalate-accumulators after cuttings or seedlings are supplied equal amounts of l-[1-14C]- or l-[UL-14C]ascorbic acid. Theoretically, l-[1-14C]ascorbic acid will produce labeled oxalic acid containing three times as much 14C as l-[UL-14C]ascorbic acid when equal amounts of label are provided. Experimentally, a ratio of 2.7 ± 0.5 is obtained in duplicate experiments with six different species. PMID:16660342

Efficient green luminescence of terbium oxalate crystals: A case study with Judd-Ofelt theory and single crystal structure analysis and the effect of dehydration on luminescence

NASA Astrophysics Data System (ADS)

Alexander, Dinu; Joy, Monu; Thomas, Kukku; Sisira, S.; Biju, P. R.; Unnikrishnan, N. V.; Sudarsanakumar, C.; Ittyachen, M. A.; Joseph, Cyriac

2018-06-01

Design and synthesis of Lanthanide based metal organic framework is a frontier area of research owing to their structural diversity enabling specific applications. The luminescence properties of rare earths, tuned by the structural features of Ln-MOFs are investigated extensively. Rare earth oxalates which can be synthesized in a facile method, ensuring the structural features of MOFs with excellent photoluminescence characteristics deserves much attention. This work is the first time report on the single crystal structure and Judd-Ofelt (JO) theoretical analysis - their correlation with the intense and sharp green luminescence of Terbium oxalate crystals. The intense green luminescence observed for Terbium oxalate crystals for a wide range of excitation from DUV to visible region despite the luminescence limiting factors are discussed. The absence of concentration quenching and lifting up of forbidden nature of f-f transitions, allowing direct excitation of Terbium ions is analysed with the help of JO theory and single crystal structure analysis. The JO analysis predicted the asymmetry of Terbium sites, allowing the electric dipole transitions and from the JO intensity parameters, promising spectroscopic parameters - emission cross section, branching ratio, gain band width and gain coefficient of the material were calculated. The single crystal structure analysis revealed the asymmetry of Tb sites and structure of Terbium oxalate is formed by the hydrogen bonded stacking of overlapped six Terbium membered rings connected by the oxalate ligands. The molecularly thick layers thus formed on the crystal surface are imaged by the atomic force microscopy. The presence of water channels in the structure and the effect of lattice water molecules on the luminescence intensity are also investigated.

Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate

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

Flynn, Elaine D.; Catalano, Jeffrey G.

Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests thatmore » this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni 2+ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni–oxalate ternary surface complexes. These observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.« less

METHOD OF MAKING ALLOYS OF SECOND RARE EARTH SERIES METALS

DOEpatents

Baker, R.D.; Hayward, B.R.

1963-01-01

>This invention relates to a process for alloying the second rare earth series metals with Mo, Nb, or Zr. A halide of the rare earth metal is mixed with about 1 to 20 at.% of an oxide of Mo, Nb, or Zr. Iodine and an alkali or alkaline earth metal are added, and the resulting mixture is heated in an inert atmosphere to 350 deg C. (AEC)

Method for treating rare earth-transition metal scrap

DOEpatents

Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.

1992-12-29

Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a prefused, rare earth fluoride-bearing flux of CaF.sub.2, CaCl.sub.2 or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy.

Method for treating rare earth-transition metal scrap

DOEpatents

Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.

1992-12-29

Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a rare earth fluoride-bearing flux of CaF[sub 2], CaCl[sub 2] or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy. 3 figs.

Rare-earth metal prices in the USA ca. 1960 to 1994

USGS Publications Warehouse

Hedrick, James B.

1997-01-01

Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass. CA, USA, in 1949, was significant because it led to the production of commercial quantities or rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

Rare-earth metal prices in the USA ca. 1960 to 1994

USGS Publications Warehouse

Hedrick, J.B.

1997-01-01

Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass, CA, USA, in 1949, was significant because it led to the production of commercial quantities of rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

Impact of Dietary Calcium and Oxalate, and Oxalobacter Formigenes Colonization on Urinary Oxalate Excretion

PubMed Central

Jiang, Juquan; Knight, John; Easter, Linda H.; Neiberg, Rebecca; Holmes, Ross P.; Assimos, Dean G.

2011-01-01

Purpose Enteric colonization with Oxalobacter formigenes, a bacterium whose main energy source is oxalate, has been demonstrated to decrease the risk of recurrent calcium oxalate kidney stone formation. We assessed the impact of diets controlled in calcium and oxalate contents on urinary and fecal analytes in healthy subjects who were naturally colonized with O. formigenes or not colonized with O. formigenes. Materials and Methods A total of 11 O. formigenes colonized and 11 noncolonized subjects were administered diets controlled in calcium and oxalate contents. We assayed 24-hour urine collections and stool samples obtained on the last 4 days of each 1-week diet for stone risk parameters and O. formigenes levels. Mixed model analysis was used to determine the effects of colonization status on these variables. Results Urinary calcium and oxalate excretion were significantly altered by the dietary changes in O. formigenes colonized and noncolonized individuals. Mixed model analysis showed significant interaction between colonization status and oxalate excretion on a low calcium (400 mg daily)/moderate oxalate (250 mg daily) diet (p = 0.026). Urinary oxalate excretion was 19.5% lower in O. formigenes colonized subjects than in noncolonized subjects on the low calcium/moderate oxalate diet (mean ± SE 34.9 ± 2.6 vs 43.6 ± 2.6 mg, p = 0.031). Conclusions Results suggest that O. formigenes colonization decreases oxalate excretion during periods of low calcium and moderate oxalate intake. PMID:21575973

ADVANCED OXIDATION: OXALATE DECOMPOSITION TESTING WITH OZONE

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

Ketusky, E.; Subramanian, K.

nearing dissolution equilibrium, and then decomposed to {le} 100 Parts per Million (ppm) oxalate. Since AOP technology largely originated on using ultraviolet (UV) light as a primary catalyst, decomposition of the spent oxalic acid, well exposed to a medium pressure mercury vapor light was considered the benchmark. However, with multi-valent metals already contained in the feed, and maintenance of the UV light a concern; testing was conducted to evaluate the impact from removing the UV light. Using current AOP terminology, the test without the UV light would likely be considered an ozone based, dark, ferrioxalate type, decomposition process. Specifically, as part of the testing, the impacts from the following were investigated: (1) Importance of the UV light on the decomposition rates when decomposing 1 wt% spent oxalic acid; (2) Impact of increasing the oxalic acid strength from 1 to 2.5 wt% on the decomposition rates; and (3) For F-area testing, the advantage of increasing the spent oxalic acid flowrate from 40 L/min (liters/minute) to 50 L/min during decomposition of the 2.5 wt% spent oxalic acid. The results showed that removal of the UV light (from 1 wt% testing) slowed the decomposition rates in both the F & H testing. Specifically, for F-Area Strike 1, the time increased from about 6 hours to 8 hours. In H-Area, the impact was not as significant, with the time required for Strike 1 to be decomposed to less than 100 ppm increasing slightly, from 5.4 to 6.4 hours. For the spent 2.5 wt% oxalic acid decomposition tests (all) without the UV light, the F-area decompositions required approx. 10 to 13 hours, while the corresponding required H-Area decompositions times ranged from 10 to 21 hours. For the 2.5 wt% F-Area sludge, the increased availability of iron likely caused the increased decomposition rates compared to the 1 wt% oxalic acid based tests. In addition, for the F-testing, increasing the recirculation flow rates from 40 liter/minute to 50 liter/minute resulted

Crystal growth methods dedicated to low solubility actinide oxalates

NASA Astrophysics Data System (ADS)

Tamain, C.; Arab-Chapelet, B.; Rivenet, M.; Grandjean, S.; Abraham, F.

2016-04-01

Two novel crystal growth syntheses dedicated to low solubility actinide-oxalate systems and adapted to glove box handling are described. These methods based on the use of precursors of either actinide metal or oxalic acid have been optimized on lanthanide systems (analogue of actinides(III)) and then assessed on real actinide systems. They allow the synthesis of several actinide oxalate single crystals, Am2(C2O4)3(H2O)3·xH2O, Th(C2O4)2·6H2O, M2+x[PuIV2-xPuIIIx(C2O4)5]·nH2O and M1-x[PuIII1-xPuIVx(C2O4)2·H2O]·nH2O. It is the first time that these well-known compounds are formed by crystal growth methods, thus enabling direct structural studies on transuranic element systems and acquisition of basic data beyond deductions from isomorphic (or not) lanthanide compounds. Characterizations by X-ray diffraction, UV-visible solid spectroscopy, demonstrate the potentialities of these two crystal growth methods to obtain oxalate compounds.

Syntheses and structures of alkaline earth metal bis(diphenylamides).

PubMed

Gärtner, Martin; Fischer, Reinald; Langer, Jens; Görls, Helmar; Walther, Dirk; Westerhausen, Matthias

2007-06-11

Various preparative procedures are employed in order to synthesize alkaline earth metal bis(diphenylamides) such as (i) metalation of HNPh2 with the alkaline earth metal M, (ii) metalation of HNPh2 with MPh2, (iii) metathesis reaction of MI2 with KNPh2, (iv) metalation of HNPh2 with PhMI in THF, and (v) metathesis reaction of PhMI with KNPh2 followed by a dismutation reaction yielding MPh2 and M(NPh2)2. The magnesium compounds [(diox)MgPh2]infinity (1) and (thf)2Mg(NPh2)2 (2) show tetracoordinate metal atoms, whereas in (dme)2Ca(NPh2)2 (3), (thf)4Sr(NPh2)2 (4), and (thf)4Ba(NPh2)2 (5) the metals are 6-fold coordinated. Additional agostic interactions between an ipso-carbon of one of the phenyl groups of the amide ligand and the alkaline earth metal atom lead to unsymmetric coordination of the NPh2 anions with two strongly different M-N-C angles in 3-5.

In vivo oxalate degradation by liposome encapsulated oxalate oxidase in rat model of hyperoxaluria

PubMed Central

Dahiya, Tulika; Pundir, C.S.

2013-01-01

Background & objectives: High level of urinary oxalate substantially increases the risk of hyperoxaluria, a significant risk factor for urolithiasis. The primary goal of this study was to reduce urinary oxalate excretion employing liposome encapsulated oxalate oxidase in animal model. Methods: A membrane bound oxalate oxidase was purified from Bougainvillea leaves. The enzyme in its native form was less effective at the physiological pH of the recipient animal. To increase its functional viability, the enzyme was immobilized on to ethylene maleic anhydride (EMA). Rats were injected with liposome encapsulated EMA- oxalate oxidase and the effect was observed on degradation of oxalic acid. Results: The enzyme was purified to apparent homogeneity with 60-fold purification and 31 per cent yield. The optimum pH of EMA-derivative enzyme was 6.0 and it showed 70 per cent of its optimal activity at pH 7.0. The EMA-bound enzyme encapsulated into liposome showed greater oxalate degradation in 15 per cent casein vitamin B6 deficient fed rats as compared with 30 per cent casein vitamin B6 deficient fed rats and control rats. Interpretation & conclusions: EMA-oxalate oxidase encapsulated liposome caused oxalate degradation in experimental hyperoxaluria indicating that the enzyme could be used as a therapeutic agent in hyperoxaluria leading to urinary stones. PMID:23481063

Hydrothermal synthesis of uranyl squarates and squarate-oxalates: hydrolysis trends and in situ oxalate formation.

PubMed

Rowland, Clare E; Cahill, Christopher L

2010-07-19

We report the synthesis of two uranyl squarates and two mixed-ligand uranyl squarate-oxalates from aqueous solutions under hydrothermal conditions. These products exhibit a range of uranyl building units from squarates with monomers in (UO(2))(2)(C(4)O(4))(5).6NH(4).4H(2)O (1; a = 16.731(17) A, b = 7.280(8) A, c = 15.872(16) A, beta = 113.294(16) degrees , monoclinic, P2(1)/c) and chains in (UO(2))(2)(OH)(2)(H(2)O)(2)(C(4)O(4)) (2; a = 12.909(5) A, b = 8.400(3) A, c = 10.322(4) A, beta = 100.056(7) degrees , monoclinic, C2/c) to two squarate-oxalate polymorphs with dimers in (UO(2))(2)(OH)(C(4)O(4))(C(2)O(4)).NH(4).H(2)O (3; a = 9.0601(7) A, b = 15.7299(12) A, c = 10.5108(8) A, beta = 106.394(1) degrees , monoclinic, P2(1)/n; and 4; a = 8.4469(6) A, b = 7.7589(5) A, c = 10.5257(7) A, beta = 105.696(1) degrees , monoclinic, P2(1)/m). The dominance at low pH of monomeric species and the increasing occurrence of oligomeric species with increasing pH suggests that uranyl hydrolysis, mUO(2)(2+) + nH(2)O right harpoon over left harpoon [(UO(2))(m)(OH)(n)](2m-n) + nH(+), has a significant role in the identity of the inorganic building unit. Additional factors that influence product assembly include in situ hydrolysis of squaric acid to oxalic acid, dynamic metal to ligand concentration, and additional binding modes resulting from the introduction of oxalate anions. These points and the effects of uranyl hydrolysis with changing pH are discussed in the context of the compounds presented herein.

ENHANCED CHEMICAL CLEANING: EFFECTIVENESS OF THE UV LAMP TO DECOMPOSE OXALATES

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

Ketusky, E.; Huff, T.; Sudduth, C.

2010-01-19

Enhanced Chemical Cleaning is a new process scheduled to begin cleaning Savannah River Site High Level Waste Tanks in 2012. It is an improvement over the current chemical cleaning method, in that it minimizes downstream impacts on the High Level Waste System. It is based on a state of the art scale removal process used on the secondary side of nuclear power plants, with modifications to accommodate the unique constraints created by the tanks. Both Enhanced Chemical Cleaning and the scale removal process are founded on dissolving metal oxides/hydroxides using oxalic acid, with subsequent oxalate decomposition via hydroxylation using ozonemore » or peroxide, and UV light as a catalyst. A divergence Enhanced Chemical Cleaning has from nuclear power scale removal is the significantly increased solids concentration during oxalate decomposition. These solids can limit the ability of the UV light to create hydroxyl radicals, either by limiting the ability of the light to penetrate through the solution, or by increasing the fouling rate on the UV light. Both will decrease the overall catalytic effectiveness, thereby decreasing the concentration of formed hydroxyl radicals. The hydroxyl radicals are the driving force behind the oxalate decomposition. To understand the impact of increased solids, testing was performed using a medium pressure UV light inside an ozone supplied Oxalate Decomposition Reactor. Using a dissolved metal sludge simulant with an initial oxalate concentration greater than 12,000 ppm, and an initial pH of about 2.0, the spent acid solution was recirculated through the reactor, while the UV light was allowed to foul. For the first few hours, the oxalate decomposition rate was about 1,300 ppm/hour. After about 3 hours, enough time for the UV lamp to foul, the oxalate decomposition rate decreased to about 500 ppm/hour. The decomposition rate then remained roughly constant for the next 16 hours. Overall, testing showed that the oxalate destruction rate

Two novel metal-organic coordination polymers based on diphosphonate and oxalate: Synthesis, structures and properties

NASA Astrophysics Data System (ADS)

Niu, Qing-Jun; Zheng, Yue-Qing; Zhou, Lin-Xia; Zhu, Hong-Lin

2015-07-01

Two 2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonato and oxalic acid bridged coordination polymers (H2en)[Co3(H2zdn)2(ox)(H2O)2] (1) and Cd2(H2zdn)(ox)0.5(H2O) (2) (2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonic acid=H5zdn; oxalic acid=H2ox) were synthesized under hydrothermal conditions and characterized by the infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA) and X-ray diffraction (XRD). Compound 1 is bridged by phosphonate anions to 1D chain, and further linked by oxalate anions to 2D layer. Compound 2 is bridged by O-P-O units of H5zdn to the layer, and then pillared by oxalate anions to generate 3D frameworks. Compound 1 shows anti-ferromagnetic behaviors analyzed with the temperature-dependent zero-field ac magnetic susceptibilities, while compound 2 exhibits an influence on the luminescent property.

Metal carboxylates with open architectures.

PubMed

Rao, C N R; Natarajan, Srinivasan; Vaidhyanathan, R

2004-03-12

The field of inorganic open-framework materials is dominated by aluminosilicates and phosphates. The metal carboxylates have emerged as an important family in the last few years. This family includes not only mono- and dicarboxylates of transition, rare-earth, and main-group metals, but also a variety of hybrid structures. Some of the carboxylates possess novel adsorption and magnetic properties. Dicarboxylates and related species provide an effective means of designing novel hybrid structures with porous and other properties. In some of these structures, the dicarboxylate acts as a linker between two inorganic units. Hybrid nanocomposites are also of particular note, for example, cadmium oxalate host lattices that can accommodate extended alkali-metal halide structures. This Review discusses the synthesis, structure, and properties of various types of open-framework metal carboxylates.

Facile fabrication of cobalt oxalate nanostructures with superior specific capacitance and super-long cycling stability

NASA Astrophysics Data System (ADS)

Cheng, Guanhua; Si, Conghui; Zhang, Jie; Wang, Ying; Yang, Wanfeng; Dong, Chaoqun; Zhang, Zhonghua

2016-04-01

Transition metal oxalate materials have shown huge competitive advantages for applications in supercapacitors. Herein, nanostructured cobalt oxalate supported on cobalt foils has been facilely fabricated by anodization, and could directly serve as additive/binder-free electrodes for supercapacitors. The as-prepared cobalt oxalate electrodes present superior specific capacitance of 1269 F g-1 at the current density of 6 A g-1 in the galvanostatic charge/discharge test. Moreover, the retained capacitance is as high as 87.2% as the current density increases from 6 A g-1 to 30 A g-1. More importantly, the specific capacitance of cobalt oxalate retains 91.9% even after super-long cycling of 100,000 cycles. In addition, an asymmetric supercapacitor assembled with cobalt oxalate (positive electrode) and activated carbon (negative electrode) demonstrates excellent capacitive performance with high energy density and power density.

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2016-06-28

The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

Influence of a low- and a high-oxalate vegetarian diet on intestinal oxalate absorption and urinary excretion.

PubMed

Thomas, E; von Unruh, G E; Hesse, A

2008-09-01

To compare quantitatively the effect of a low- and a high-oxalate vegetarian diet on intestinal oxalate absorption and urinary excretion. Eight healthy volunteers (three men and five women, mean age 28.6+/-6.3) were studied. Each volunteer performed the [(13)C(2)]oxalate absorption test thrice on a low-oxalate mixed diet, thrice on a low-oxalate vegetarian diet and thrice on a high-oxalate vegetarian diet. For each test, the volunteers had to adhere to an identical diet and collect their 24-h urines. In the morning of the second day, a capsule containing [(13)C(2)]oxalate was ingested. On the low-oxalate vegetarian diet, mean intestinal oxalate absorption and urinary oxalate excretion increased significantly to 15.8+/-2.9% (P=0.012) and 0.414+/-0.126 mmol/day (P=0.012), compared to the mixed diet. On the high-oxalate vegetarian diet, oxalate absorption (12.5+/-4.6%, P=0.161) and urinary excretion (0.340+/-0.077 mmol/day, P=0.093) did not change significantly, compared to the mixed diet. A vegetarian diet can only be recommended for calcium oxalate stone patients, if the diet (1) contains the recommended amounts of divalent cations such as calcium and its timing of ingestion to a meal rich in oxalate is considered and (2) excludes foodstuffs with a high content of nutritional factors, such as phytic acid, which are able to chelate calcium.

Applications in environmental bioinorganic: Nutritional and ultrastructural evaluation and calculus of thermodynamic and structural properties of metal-oxalate complexes.

PubMed

Tolentino, Terezinha Alves; Bertoli, Alexandre Carvalho; dos Santos Pires, Maíra; Carvalho, Ruy; Labory, Claudia Regina Gontijo; Nunes, Janaira Santana; Bastos, Ana Rosa Ribeiro; de Freitas, Matheus Puggina

2015-01-01

Lead (Pb) is known by its toxicity both for animals and plants. In order to evaluate its toxicity, plants of Brachiaria brizantha were cultivated on nutritive solution of Hoagland during 90 days and submitted to different concentrations of Pb. The content of macro and micronutrients was evaluated and there was a reduction on root content of Ca, besides the lowest dosages of Pb had induced an increase of N, S, Mn, Cu, Zn and Fe. The cell ultrastructure of leaves and roots were analyzed by transmission electronic microscopy (TEM). Among the main alterations occurred there were invaginations on cell walls, the presence of crystals on the root cells, accumulation of material on the interior of cells and vacuolar compartmentalization. On the leaves the degradation of chloroplasts was observed, as well as the increase of vacuoles. Structures for the formation of oxalate crystals were proposed through molecular modeling and thermodynamic stability. Calculi suggest the formation of highly stable metal-oxalate complexes. Copyright © 2015 Elsevier B.V. All rights reserved.

Thermophysical properties of liquid rare earth metals

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Sonvane, Y. A.; Patel, H. P.; Jani, A. R.

2013-06-01

The thermodynamical properties like long wavelength limit S(0), iso-thermal compressibility (χT), thermal expansion coefficient (αV), thermal pressure coefficient (γV), specific heat at constant volume (CV) and specific heat at constant pressure (CP) are calculated for liquid rare earth metals. Our newly constructed parameter free model potential is used to describe the electron ion interaction due to Sarkar et al (S) local field correction function. Lastly, we conclude that our newly constructed model potential is capable to explain the thermophysical properties of liquid rare earth metals.

Artificial photosynthesis of oxalate and oxalate-based polymer by a photovoltaic reactor

PubMed Central

Nong, Guangzai; Chen, Shan; Xu, Yuanjin; Huang, Lijie; Zou, Qingsong; Li, Shiqiang; Mo, Haitao; Zhu, Pingchuan; Cen, Weijian; Wang, Shuangfei

2014-01-01

A photovoltaic reactor was designed for artificial photosynthesis, based on the reactions involved in high energy hydrogen atoms, which were produced from water electrolysis. Water and CO2, under the conditions studied, were converted to oxalate (H2C2O4) and a polymer. This was the first time that the oxalates and oxalate-based polymer were produced from the artificial photosynthesis process. PMID:24389750

Vibrational studies in aqueous solutions. Part II. The acid oxalate ion and oxalic acid

NASA Astrophysics Data System (ADS)

Shippey, T. A.

1980-08-01

Assignments for oxalic acid in solution are re-examined. A detailed assignment of the IR and Raman spectra of the acid oxalate ion is presented for the first time. Raman spectroscopy is used to study the first ionization of oxalic acid.

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

Selective adsorption in two porous triazolate–oxalate-bridged antiferromagnetic metal-azolate frameworks obtained via in situ decarboxylation of 3-amino-1,2,4-triazole-5-carboxylic acid

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

Hou, Juan-Juan; Xu, Xia; Jiang, Ning

2015-03-15

Solvothermal reactions of metal salts, 3-amino-1,2,4-triazole-5-carboxylic acid (H{sub 2}atzc) and ammonium oxalate in different temperature produced two metal azolate frameworks, namely, [Cu{sub 3}(atzc){sub 2}(atz)(ox)]·1.5H{sub 2}O (1) and [Co{sub 5}(atz){sub 4}(ox){sub 3}(HCOO){sub 2}]·DMF (2) (H{sub 2}atzc=3-amino-1,2,4-triazole-5-carboxylic acid, Hatz=3-amino-1,2,4-triazole, and ox=oxalate), in which the atzc precusor was in situ decarboxylated. Structural determination reveals that 1 contains [Cu{sub 3}(atzc){sub 2}(atz)]{sup 2−} layers of mixed μ{sub 4}-atzc and μ{sub 3}-atz ligands, which are pillared by ox{sup 2−} groups to form a 3D porous framework. Compound 2 contains 2D layers with basic spindle-shaped decanuclear units, which extended by ox{sup 2−} and formates to form 3Dmore » porous framework. Gas adsorption investigation revealed that two kinds of frameworks exhibited selective CO{sub 2} over N{sub 2} sorption. Moreover, activated 2 shows H{sub 2} storage capacity. Additionally, magnetic properties of both the compounds have been investigated. - Graphical abstract: Solvothermal reactions of metal salts, 3-amino-1,2,4-triazole-5-carboxylate and oxalate produced two metal azolate frameworks, which could store gas molecules, especially H{sub 2} due to small pores. in situ decarboxylation of precursor was observed. - Highlights: • Two MAFs were synthesized via in situ decarboxylation of H{sub 2}atzc. • Both activated frameworks exhibited selective CO{sub 2} over N{sub 2} sorption. • Activated 2 could adsorb H{sub 2}, which makes it promising candidates for gas storage.« less

Metal Based Synthetic Strategies and the Examination of Structure Determining Factors in Alkaline Earth Metal Compounds

NASA Astrophysics Data System (ADS)

Takahashi, Yuriko

Last decades have witnessed a large expansion of the organometallic heavier alkaline earth metal species. However, continued growth of this promising area of chemistry has been slowed by severe restrictions and limitations in viable synthetic methodologies leading to difficulties in preparing and characterizing the target compounds. There is clearly a need for the further development of synthetic methodologies and detailed structure function analysis that will promote the further advancement of organoalkaline earth metal chemistry in applications as diverse as materials chemistry and catalysis. This thesis work greatly extends the synthetic options currently available towards organoalkaline earth metal species by introducing redox transmetallation protolysis (RTP), a reaction based on the readily available Ph3Bi as a non-toxic transmetallation agent. Based on a straightforward one-pot procedure and work-up, Ph3Bi based RTP presents a powerful synthetic alternative for the facile preparation of a large variety of heavy alkaline earth metal compounds. The second part of the thesis explores the effect of secondary non covalent interactions on the coordination chemistry as well as thermal properties of a series of novel alkali, alkaline earth, rare earth as well as heterobimetallic alkali/alkaline earth fluoroalkoxides. These compounds showcase the significance of non-covalent M···F-C and agostic interactions on metal stabilization and structural features, providing critical input on ligand design for the design of advanced metal organic vapor deposition (MOCVD) precursor materials. This work also showcases the impact of M···F-C interactions over M---co-ligand coordination, a critical precursor design element as well.

High variability of the heterogeneous ice nucleation potential of oxalic acid dihydrate and sodium oxalate

NASA Astrophysics Data System (ADS)

Wagner, R.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Leisner, T.

2010-04-01

The heterogeneous ice nucleation potential of airborne oxalic acid dihydrate and sodium oxalate particles in the deposition and condensation mode has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 244 and 228 K. Previous laboratory studies have highlighted the particular role of oxalic acid dihydrate as the only species amongst a variety of other investigated dicarboxylic acids to be capable of acting as a heterogeneous ice nucleus in both the deposition and immersion mode. We could confirm a high deposition mode ice activity for 0.03 to 0.8 μm sized oxalic acid dihydrate particles that were either formed by nucleation from a gaseous oxalic acid/air mixture or by rapid crystallisation of highly supersaturated aqueous oxalic acid solution droplets. The critical saturation ratio with respect to ice required for deposition nucleation was found to be less than 1.1 and the size-dependent ice-active fraction of the aerosol population was in the range from 0.1 to 22%. In contrast, oxalic acid dihydrate particles that had crystallised from less supersaturated solution droplets and had been allowed to slowly grow in a supersaturated environment from still unfrozen oxalic acid solution droplets over a time period of several hours were found to be much poorer heterogeneous ice nuclei. We speculate that under these conditions a crystal surface structure with less-active sites for the initiation of ice nucleation was generated. Such particles partially proved to be almost ice-inactive in both the deposition and condensation mode. At times, the heterogeneous ice nucleation ability of oxalic acid dihydrate significantly changed when the particles had been processed in preceding cloud droplet activation steps. Such behaviour was also observed for the second investigated species, namely sodium oxalate. Our experiments address the atmospheric scenario that coating layers

High variability of the heterogeneous ice nucleation potential of oxalic acid dihydrate and sodium oxalate

NASA Astrophysics Data System (ADS)

Wagner, R.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Leisner, T.

2010-08-01

The heterogeneous ice nucleation potential of airborne oxalic acid dihydrate and sodium oxalate particles in the deposition and condensation mode has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 244 and 228 K. Previous laboratory studies have highlighted the particular role of oxalic acid dihydrate as the only species amongst a variety of other investigated dicarboxylic acids to be capable of acting as a heterogeneous ice nucleus in both the deposition and immersion mode. We could confirm a high deposition mode ice activity for 0.03 to 0.8 μm sized oxalic acid dihydrate particles that were either formed by nucleation from a gaseous oxalic acid/air mixture or by rapid crystallisation of highly supersaturated aqueous oxalic acid solution droplets. The critical saturation ratio with respect to ice required for deposition nucleation was found to be less than 1.1 and the size-dependent ice-active fraction of the aerosol population was in the range from 0.1 to 22%. In contrast, oxalic acid dihydrate particles that had crystallised from less supersaturated solution droplets and had been allowed to slowly grow in a supersaturated environment from still unfrozen oxalic acid solution droplets over a time period of several hours were found to be much poorer heterogeneous ice nuclei. We speculate that under these conditions a crystal surface structure with less-active sites for the initiation of ice nucleation was generated. Such particles partially proved to be almost ice-inactive in both the deposition and condensation mode. At times, the heterogeneous ice nucleation ability of oxalic acid dihydrate significantly changed when the particles had been processed in preceding cloud droplet activation steps. Such behaviour was also observed for the second investigated species, namely sodium oxalate. Our experiments address the atmospheric scenario that coating layers

Oxalate and phytate of soy foods.

PubMed

Al-Wahsh, Ismail A; Horner, Harry T; Palmer, Reid G; Reddy, Manju B; Massey, Linda K

2005-07-13

The consumption of foods made from soybeans is increasing because of their desirable nutritional value. However, some soy foods contain high concentrations of oxalate and/or phytate. Oxalate is a component of calcium oxalate kidney stones, whereas phytate is an inhibitor of calcium kidney stone formation. Thirty tested commercial soy foods exhibited ranges of 0.02-2.06 mg oxalate/g and 0.80-18.79 mg phytate/g. Commercial soy foods contained 2-58 mg of total oxalate per serving and 76-528 mg phytate per serving. Eighteen of 19 tofu brands and two soymilk brands contained less than 10 mg oxalate per serving, defined as a low oxalate food. Soy flour, textured vegetable soy protein, vegetable soybeans, soy nuts, tempeh, and soynut butter exhibited greater than 10 mg per serving. The correlation between oxalate and phytate in the soy foods was significant (r = 0.71, P < 0.001) indicating that oxalate-rich soy foods also contain higher concentrations of phytate. There also was a significant correlation, based on molar basis, between the divalent ion binding potential of oxalate plus phytate and calcium plus magnesium (r = 0.90, P < 0.001) in soy foods. Soy foods containing small concentrations of oxalate and moderate concentrations of phytate may be advantageous for kidney stone patients or persons with a high risk of kidney stones.

Metabolic Conversion of l-Ascorbic Acid to Oxalic Acid in Oxalate-accumulating Plants 1

PubMed Central

Yang, Joan C.; Loewus, Frank A.

1975-01-01

l-Ascorbic acid-1-14C and its oxidation product, dehydro-l-ascorbic acid, produced labeled oxalic acid in oxalate-accumulating plants such as spinach seedlings (Spinacia oleracea) and the detached leaves of woodsorrel (Oxalis stricta and O. oregana), shamrock (Oxalis adenopylla), and begonia (Begonia evansiana). In O. oregana, conversion occurred equally well in the presence or absence of light. This relationship between l-ascorbic acid metabolism and oxalic acid formation must be given careful consideration in attempts to explain oxalic accumulation in plants. PMID:16659288

Oxalate content of cereals and cereal products.

PubMed

Siener, Roswitha; Hönow, Ruth; Voss, Susanne; Seidler, Ana; Hesse, Albrecht

2006-04-19

Detailed knowledge of food oxalate content is of essential importance for dietary treatment of recurrent calcium oxalate urolithiasis. Dietary oxalate can contribute considerably to the amount of urinary oxalate excretion. Because cereal foods play an important role in daily nutrition, the soluble and total oxalate contents of various types of cereal grains, milling products, bread, pastries, and pasta were analyzed using an HPLC-enzyme-reactor method. A high total oxalate content (>50 mg/100 g) was found in whole grain wheat species Triticum durum (76.6 mg/100 g), Triticum sativum (71.2 mg/100 g), and Triticum aestivum (53.3 mg/100 g). Total oxalate content was comparably high in whole grain products of T. aestivum, that is, wheat flakes and flour, as well as in whole grain products of T. durum, that is, couscous, bulgur, and pasta. The highest oxalate content was demonstrated for wheat bran (457.4 mg/100 g). The higher oxalate content in whole grain than in refined grain cereals suggests that oxalic acid is primarily located in the outer layers of cereal grains. Cereals and cereal products contribute to the daily oxalate intake to a considerable extent. Vegetarian diets may contain high amounts of oxalate when whole grain wheat and wheat products are ingested. Recommendations for prevention of recurrence of calcium oxalate stone disease have to take into account the oxalate content of these foodstuffs.

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

Oxalate analysis methodology for decayed wood

Treesearch

Carol A. Clausen; William Kenealy; Patricia K. Lebow

2008-01-01

Oxalate from partially decayed southern pine wood was analyzed by HPLC or colorimetric assay. Oxalate extraction efficiency, assessed by comparing analysis of whole wood cubes with ground wood, showed that both wood geometries could be extracted with comparable efficiency. To differentiate soluble oxalate from total oxalate, three extraction methods were assessed,...

Multiscale structural characterizations of mixed U(iv)-An(iii) oxalates (An(iii) = Pu or Am) combining XAS and XRD measurements.

PubMed

Arab-Chapelet, B; Martin, P M; Costenoble, S; Delahaye, T; Scheinost, A C; Grandjean, S; Abraham, F

2016-04-28

Mixed actinide(III,IV) oxalates of the general formula M2.2UAn(C2O4)5·nH2O (An = Pu or Am and M = H3O(+) and N2H5(+)) have been quantitatively precipitated by oxalic precipitation in nitric acid medium (yield >99%). Thorough multiscale structural characterization using XRD and XAS measurements confirmed the existence of mixed actinide oxalate solid solutions. The XANES analysis confirmed that the oxidation states of the metallic cations, tetravalent for uranium and trivalent for plutonium and americium, are maintained during the precipitation step. EXAFS measurements show that the local environments around U(+IV), Pu(+III) and Am(+III) are comparable, and the actinides are surrounded by ten oxygen atoms from five bidentate oxalate anions. The mean metal-oxygen distances obtained by XAS measurements are in agreement with those calculated from XRD lattice parameters.

Natural abiotic formation of oxalic acid in soils: results from aromatic model compounds and soil samples.

PubMed

Studenroth, Sabine; Huber, Stefan G; Kotte, Karsten; Schöler, Heinz F

2013-02-05

Oxalic acid is the smallest dicarboxylic acid and plays an important role in soil processes (e.g., mineral weathering and metal detoxification in plants). We have first proven its abiotic formation in soils and investigated natural abiotic degradation processes based on the oxidation of soil organic matter, enhanced by Fe(3+) and H(2)O(2) as hydroxyl radical suppliers. Experiments with the model compound catechol and further hydroxylated benzenes were performed to examine a common degradation pathway and to presume a general formation mechanism of oxalic acid. Two soil samples were tested for the release of oxalic acid and the potential effects of various soil parameters on oxalic acid formation. Additionally, the soil samples were treated with different soil sterilization methods to prove the oxalic acid formation under abiotic soil conditions. Different series of model experiments were conducted to determine a range of factors including Fe(3+), H(2)O(2), reaction time, pH, and chloride concentration on oxalic acid formation. Under certain conditions, catechol is degraded up to 65.6% to oxalic acid referring to carbon. In serial experiments with two soil samples, oxalic acid was produced, and the obtained results are suggestive of an abiotic degradation process. In conclusion, Fenton-like conditions with low Fe(3+) concentrations and an excess of H(2)O(2) as well as acidic conditions were required for an optimal oxalic acid formation. The presence of chloride reduced oxalic acid formation.

Fish Oil Supplementation and Urinary Oxalate Excretion in Normal Subjects on a Low-oxalate Diet

PubMed Central

Lange, Jessica N.; Mufarrij, Patrick W.; Easter, Linda; Knight, John; Holmes, Ross P.; Assimos, Dean G.

2014-01-01

OBJECTIVE To determine if fish oil supplementation reduces endogenous oxalate synthesis in healthy subjects. MATERIALS AND METHODS Fifteen healthy non–stone-forming adults participated in this study. Subjects first abstained from using vitamins, medications, or foods enriched in omega-3 fatty acids for 30 days. Next, they collected two 24-hour urine specimens while consuming a self-selected diet. Subjects consumed an extremely low-oxalate and normal-calcium diet for 5 days and collected 24-hour urine specimens on the last 3 days of this diet. Next, the subjects took 2 fish oil capsules containing 650-mg eicosapentaenoic acid and 450-mg docosahexaenoic acid twice daily for 30 days. They consumed a self-selected diet on days 1–25 and the controlled diet on days 26–30. Twenty-four-hour urine samples were collected on days 28–30. Excretion levels of urinary analytes including oxalate and glycolate were analyzed. RESULTS Although there was a significant reduction in urinary oxalate, magnesium, and potassium excretions and an increase in uric acid excretion during the controlled dietary phases compared with the self-selected diet, there were no significant differences in their excretion during controlled diet phases with and without fish oil supplementation. CONCLUSION These results suggest that fish oil supplementation does not reduce endogenous oxalate synthesis or urinary oxalate excretion in normal adults during periods of extremely low oxalate intake. However, these results do not challenge the previously described reduction in urinary oxalate excretion demonstrated in normal subjects consuming a moderate amount of oxalate in conjunction with fish oil. PMID:25102784

Gut microbiota and oxalate homeostasis

PubMed Central

2017-01-01

This perspective focuses on how the gut microbiota can impact urinary oxalate excretion in the context of hyperoxaluria, a major risk factor in kidney stone disease. In the genetic disease of Primary Hyperoxaluria Type 1 (PH1), an increased endogenous production of oxalate, due to a deficiency of the liver enzyme alanine-glyoxylate aminotransferase (AGT), results in hyperoxaluria and oxalate kidney stones. The constant elevation in urinary oxalate in PH1 patients ultimately leads to tissue deposition of oxalate, renal failure and death and the only known cure for PH1 is a liver or liver-kidney transplant. The potential impact of a probiotic/therapeutic approach may be clinically significant in PH1 and could also extend to a much larger population of idiopathic oxalate stone formers who comprise ~12% of Americans, individuals with enteric hyperoxaluria, and an emerging population of hyperoxaluric patients who have undergone bariatric surgery and develop kidney stone disease as a consequence. PMID:28217701

Gut microbiota and oxalate homeostasis.

PubMed

Hatch, Marguerite

2017-01-01

This perspective focuses on how the gut microbiota can impact urinary oxalate excretion in the context of hyperoxaluria, a major risk factor in kidney stone disease. In the genetic disease of Primary Hyperoxaluria Type 1 (PH1), an increased endogenous production of oxalate, due to a deficiency of the liver enzyme alanine-glyoxylate aminotransferase (AGT), results in hyperoxaluria and oxalate kidney stones. The constant elevation in urinary oxalate in PH1 patients ultimately leads to tissue deposition of oxalate, renal failure and death and the only known cure for PH1 is a liver or liver-kidney transplant. The potential impact of a probiotic/therapeutic approach may be clinically significant in PH1 and could also extend to a much larger population of idiopathic oxalate stone formers who comprise ~12% of Americans, individuals with enteric hyperoxaluria, and an emerging population of hyperoxaluric patients who have undergone bariatric surgery and develop kidney stone disease as a consequence.

Rare-Earth Metals and Their Applications in Aviation

DTIC Science & Technology

1984-08-01

metals are not as common as iron and steel which are visible everywhere, yet they are not unfamiliar to us. We often encounter them in everyday life...the flint of a lighter. It is an alloy of rare-earth metal and iron . It contains about 30% iron and the remainder is a composite rare-earth alloy...used to manufacture the detonators of bullets and shells as well as the pyrophoric alloys of firing devices. This type of alloy has a 49.5% content of

Oxalate, inflammasome, and progression of kidney disease

PubMed Central

Ermer, Theresa; Eckardt, Kai-Uwe; Aronson, Peter S.; Knauf, Felix

2016-01-01

Purpose of review Oxalate is an end product of metabolism excreted via the kidney. Excess urinary oxalate, whether from primary or enteric hyperoxaluria, can lead to oxalate deposition in the kidney. Oxalate crystals are associated with renal inflammation, fibrosis and progressive renal failure. It has long been known that as glomerular filtration rate (GFR) becomes reduced in chronic kidney disease (CKD), there is striking elevation of plasma oxalate. Taken together, these findings raise the possibility that elevation of plasma oxalate in CKD may promote renal inflammation and more rapid progression of CKD independent of primary etiology. Recent findings The inflammasome has recently been identified to play a critical role in oxalate-induced renal inflammation. Oxalate crystals have been shown to activate the nucleotide-binding domain, leucine-rich repeat inflammasome 3 (also known as NALP3, NLRP3 or cryopyrin), resulting in release of Interleukin-1β and macrophage infiltration. Deletion of inflammasome proteins in mice protects from oxalate-induced renal inflammation and progressive renal failure. Summary The findings reviewed in this article expand our understanding of the relevance of elevated plasma oxalate levels leading to inflammasome activation. We propose that inhibiting oxalate-induced inflammasome activation, or lowering plasma oxalate, may prevent or mitigate progressive renal damage in CKD, and warrants clinical trials. PMID:27191349

The bioavailability of oxalate from Oca (Oxalis tuberosa).

PubMed

Albihn, P B; Savage, G P

2001-08-01

It is believed that soluble oxalate has higher bioavailability than insoluble oxalate. Oca (Oxalis tuberosa) is moderately high in oxalate and contains oxalate in soluble form only. We estimated the bioavailability of oxalate in oca based on the urinary excretion of oxalate after oxalate loading with oca to estimate the bioavailability of oxalate in oca. We also clarified whether bioavailability differs in various oxalate loads from the same food source and studied the effect of an additional calcium source on the bioavailability of oxalate from oca. Four men and 4 women ingested 50, 100 and 150 gm. oca as well as 100 gm. oca with 100 gm. sour cream. Oxalate was measured in a 6-hour urine sample from each volunteer. The mean bioavailability of oxalate from oca plus or minus standard deviation was 1.44% +/- 1.31% during the 6-hour period after intake. There was no significant difference in oxalate bioavailability among oxalate intake levels in this study, although oca consumption with sour cream significantly decreased the uptake of oxalate (p <0.01). The variation in bioavailability among individuals was high in our study. The bioavailability of oxalate in oca appears to be similar to that in spinach. However, bioavailability varies among individuals and depends on other constituents of a combined meal.

Ascorbic Acid Intake and Oxalate Synthesis

PubMed Central

Knight, John; Madduma-Liyanage, Kumudu; Mobley, James A.; Assimos, Dean G.; Holmes, Ross P.

2016-01-01

In humans approximately 60 mg of ascorbic acid (AA) breaks down in the body each day and has to be replaced by a dietary intake of 70 mg in females and 90 mg in males to maintain optimal health and AA homeostasis. The breakdown of AA is non-enzymatic and results in oxalate formation. The exact amount of oxalate formed has been difficult to ascertain primarily due to the limited availability of healthy human tissue for such research and the difficulty in measuring AA and its breakdown products. The breakdown of 60 mg of AA to oxalate could potentially result in the formation of up to 30 mg oxalate per day. This exceeds our estimates of the endogenous production of 10 – 25 mg oxalate per day, indicating that degradative pathways that do not form oxalate exist. In this review we examine what is known about the pathways of AA metabolism and how oxalate forms. We further identify how gaps in our knowledge may be filled to more precisely determine the contribution of AA breakdown to oxalate production in humans. The use of stable isotopes of AA to directly assess the conversion of vitamin to oxalate should help fill this void. PMID:27002809

Oxalate minerals on Mars?

NASA Astrophysics Data System (ADS)

Applin, D. M.; Izawa, M. R. M.; Cloutis, E. A.; Goltz, D.; Johnson, J. R.

2015-06-01

Small amounts of unidentified organic compounds have only recently been inferred on Mars despite strong reasons to expect significant concentrations and decades of searching. Based on X-ray diffraction and reflectance spectroscopic analyses we show that solid oxalic acid and its most common mineral salts are stable under the pressure and ultraviolet irradiation environment of the surface of Mars, and could represent a heretofore largely overlooked reservoir of organic carbon in the martian near-surface. In addition to the delivery to Mars by carbonaceous chondrites, oxalate minerals are among the predicted breakdown products of meteoritic organic matter delivered to the martian surface, as well as any endogenic organic carbon reaching the martian surface from the interior. A reinterpretation of pyrolysis experiments from the Viking, Phoenix, and Mars Science Laboratory missions shows that all are consistent with the presence of significant concentrations of oxalate minerals. Oxalate minerals could be important in numerous martian geochemical processes, including acting as a possible nitrogen sink (as ammonium oxalate), and contributing to the formation of “organic” carbonates, methane, and hydroxyl radicals.

Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

PubMed

Meshram, Pratima; Pandey, B D; Mankhand, T R

2016-05-01

Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features. Copyright © 2015. Published by Elsevier Ltd.

The abiotic degradation of soil organic matter to oxalic acid

NASA Astrophysics Data System (ADS)

Studenroth, Sabine; Huber, Stefan; Schöler, H. F.

2010-05-01

The abiotic degradation of soil organic matter to volatile organic compounds was studied intensely over the last years (Keppler et al., 2000; Huber et al., 2009). It was shown that soil organic matter is oxidised due to the presence of iron (III), hydrogen peroxide and chloride and thereby produces diverse alkyl halides, which are emitted into the atmosphere. The formation of polar halogenated compounds like chlorinated acetic acids which are relevant toxic environmental substances was also found in soils and sediments (Kilian et al., 2002). The investigation of the formation of other polar halogenated and non-halogenated compounds like diverse mono- and dicarboxylic acids is going to attain more and more importance. Due to its high acidity oxalic acid might have impacts on the environment e.g., nutrient leaching, plant diseases and negative influence on microbial growth. In this study, the abiotic formation of oxalic acid in soil is examined. For a better understanding of natural degradation processes mechanistic studies were conducted using the model compound catechol as representative for structural elements of the humic substances and its reaction with iron (III) and hydrogen peroxide. Iron is one of the most abundant elements on earth and hydrogen peroxide is produced by bacteria or through incomplete reduction of oxygen. To find suitable parameters for an optimal reaction and a qualitative and quantitative analysis method the following reaction parameters are varied: concentration of iron (III) and hydrogen peroxide, time dependence, pH-value and influence of chloride. Analysis of oxalic acid was performed employing an ion chromatograph equipped with a conductivity detector. The time dependent reaction shows a relatively fast formation of oxalic acid, the optimum yield is achieved after 60 minutes. Compared to the concentration of catechol an excess of hydrogen peroxide as well as a low concentration of iron (III) are required. In absence of chloride the

METHOD OF SEPARATING RARE EARTHS BY ION EXCHANGE

DOEpatents

Spedding, F.H.; Powell, J.E.

1960-10-18

A process is given for separating yttrium and rare earth values having atomic numbers of from 57 through 60 and 68 through 71 from an aqueous solution whose pH value can range from 1 to 9. All rare earths and yttrium are first adsorbed on a cation exchange resin, and they are then eluted with a solution of N-hydroxyethylethylenediaminetriacetic acid (HEDTA) in the order of decreasing atomic number, yttrium behaving like element 61; the effluents are collected in fractions. The HEDTA is recovered by elution with ammonia solution and the resin is regenerated with sulfuric acid. Rare earths are precipitated from the various effluents with oxalic acid, and each supernatant is passed over cation exchange resin for adsorption of HEDTA and nonprecipitated rare earths: the oxalic acid is not retained by the resin.

Comparison of sulfuric and oxalic acid anodizing for preparation of thermal control coatings for spacecraft

NASA Technical Reports Server (NTRS)

Le, Huong G.; Watcher, John M.; Smith, Charles A.

1988-01-01

The development of thermal control surfaces, which maintain stable solar absorptivity and infrared emissivity over long periods, is challenging due to severe conditions in low-Earth orbit (LEO). Some candidate coatings are second-surface silver-coated Teflon; second-surface, silvered optical solar reflectors made of glass or quartz; and anodized aluminum. Sulfuric acid anodized and oxalic acid anodized aluminum was evaluated under simulated LEO conditions. Oxalic acid anodizing shows promise of greater stability in LEO over long missions, such as the 30 years planned for the Space Station. However, sulfuric acid anodizing shows lower solar absorptivity.

Determination of urine oxalate level in rats with renal calcium oxalate calculus by high-performance liquid chromatography.

PubMed

Cao, Qiu-shi; Ba, Yuan-ming; Luo, Jun-hua; Dai, Qi

2015-02-01

To establish a method of high-performance liquid chromatography (HPLC) for determining the urine oxalate levle in rats with renal calcium oxalate calculus. Totally 24 SPF Wistar healthy male rats were randomly divided into control group(n=12)and ethylene glycol (EG) group (n=12). Rats in EG group were administered intragastrically with 2% ammonium chloride (AC)2 ml/rat per day+1% ethylene glycol (EG), along with free access to drinking water.The control group was fed with deionized water, along with the intragastric administration of normal saline (1 ml per day). Twenty-eight days after modelling, the 24-hour urine samples were collected, and the urine oxalic acid levels were determined using HPLC and the results were compared with those of catalytic spectrophotometry using oxidation of methyl. During the HPLC, the samples were separated on Aglient 5TC-C18 (250×4.6 mm,5 Μm), eluted with mixture of methanol (0.1 mol/L) and ammonium acetate (15:85) at 1.2 ml/min, and detected at 314 nm, with the column temperature being 20 ℃. The standard curves of high and low concentrations of oxalic acid were y=5909.1x+378730, R² =0.9984 and y=7810.5x-16635, R² =0.9967,respectively. The lowest detectable concentration in this method was 5 Μg/ml. The linear high concentration range of oxalate stood at 62.50-2000.00 Μg/ml, and the linear low concentration range of oxalate stood at 6.25-100.00 Μg/ml. Its average recovery was 95.1%, and its within-day and day-to-day precisions were 3.4%-10.8% and 3.8%-9.4%. Both HPLC and catalytic spectrophotometry showed significantly higher urinary oxalic acid concentration and 24 h urine oxalate level in EG group compared with the control group [urinary oxalic acid concentration: (736.35 ± 254.52) Μg/ml vs.(51.56 ± 36.34) Μg/ml,(687.35 ± 234.53) Μg/ml vs.(50.24 ± 42.34) Μg/ml;24 h urine oxalate level: (11.23 ± 4.12)mg vs.(0.87 ± 0.45)mg,(9.89 ± 3.55)mg vs. (0.77 ± 0.65)mg; all P<0.01]. No statistically significant difference

An oxalyl-CoA dependent pathway of oxalate catabolism plays a role in regulating calcium oxalate crystal accumulation and defending against oxalate-secreting phytopathogens in Medicago truncatula

USDA-ARS?s Scientific Manuscript database

Considering the widespread occurrence of oxalate in nature and its broad impact on a host of organisms, it is surprising that so little is known about the turnover of this important acid. In plants, oxalate oxidase is the most well studied enzyme capable of degrading oxalate, but not all plants pos...

Crystallographic phases in heavy rare earth metals under megabar pressures

NASA Astrophysics Data System (ADS)

Samudrala, G. K.; Vohra, Y. K.

2012-07-01

Experiments aimed at understanding the crystallographic phases of heavy rare earth metals were carried out in a diamond anvil cell at the Advanced Photon Source, Argonne National Laboratory. Heavy rare earth metals dysprosium (Dy), holmium (Ho), erbium (Er) and thulium (Tm) were compressed to multi-megabar pressures. The rare earth crystal sequence hcp→Sm-type→dhcp→distorted-fcc (dfcc) is observed in all four elements. Upon further compression, a structural transformation to a monoclinic C2/m phase has been observed. We summarize the results from these experiments and present Rietveld structural refinements on high pressure phases for the specific case of dysprosium.

A novel 3D framework indium phosphite-oxalate based on a pcu-type topology

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

Zuo, Mengmeng; Zhou, Mingdong; Hu, Dianwen

2016-05-15

A new inorganic–organic hybrid indium phosphite-oxalate, formulated as H[In{sub 5}(HPO{sub 3}){sub 6}(H{sub 2}PO{sub 3}){sub 2}(C{sub 2}O{sub 4}){sub 2}]·(C{sub 4}N{sub 2}H{sub 11}){sub 2}·H{sub 2}O 1 has been hydrothermally synthesized in the presence of piperazine acting as a structure directing agent (SDA). The single crystal X-ray diffraction reveals that compound 1 shows three-dimensional open-framework with intersecting 12-ring channels along the [010] and [001] directions, which is constructed from strictly alternating double 6-ring units (D6Rs), [C{sub 2}O{sub 4}]{sup 2−} groups and [H{sub 2}PO{sub 3}]{sup −} pseudo-pyramids. It is noted that the classical D6R SBU is firstly reported in main metal phosphite/phosphite-oxalate. By regardingmore » D6R as the 6-connected nodes, the inorganic–organic hybrid framework is based on a pcu-type topology. The as-synthesized product was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA), ICP-AES and elemental analyses. - Graphical abstract: A 3D open-framework indium phosphite-oxalate has been synthesized under hydrothermal conditions. A classical SBU, D6R, is present in the structure. By regarding D6R as the 6-connected nodes, the inorganic–organic hybrid framework is based on a pcu-type topology. - Highlights: • A new indium phosphite-oxalate based on a pcu-type topology has been synthesized. • A classical SBU, D6R, is present in the structure. • The classical SBU is firstly reported in main metal phosphite/phosphite-oxalate.« less

Heterogeneous photochemistry of oxalic acid on Mauritanian sand and Icelandic volcanic ash.

PubMed

Styler, Sarah A; Donaldson, D J

2012-08-21

Teragram quantities of crustal and volcanic aerosol are released into the atmosphere on an annual basis. Although these substrates contain photoactive metal oxides, little is known about the role that they may play in catalyzing the heterogeneous phototransformation of semivolatile organic species. In the present study, we have investigated oxalic acid photochemistry at the surface of Fe(2)O(3), TiO(2), Mauritanian sand, and Icelandic volcanic ash in the presence and absence of oxygen using a photochemical Knudsen cell reactor. Illumination of all sample types resulted in the production of gas-phase CO(2). In the case of Mauritanian sand, the production of gas-phase CO(2) scaled with the loss of surface oxalic acid. In the absence of oxygen, the production of CO(2) by the sand and ash films scaled with the absorption spectrum of iron oxalate, which suggests that the reaction is at least in part iron-mediated. The presence of oxygen suppressed CO(2) production at the Fe(2)O(3) surface, enhanced CO(2) production at the Mauritanian sand surface, and did not have a net effect upon CO(2) production at the Icelandic ash surface. These different oxygen dependencies imply that oxalic acid photochemistry at the authentic surfaces under study was not solely iron-mediated. Experiments at the TiO(2) surface, which showed enhanced CO(2) production from oxalic acid in the presence of oxygen, suggest that Ti-mediated photochemistry played an important role. In summary, these results provide evidence that solid-phase aerosol photochemistry may influence the atmospheric lifetime of oxalic acid in arid regions, where its removal via wet deposition is insignificant.

The comparability of oxalate excretion and oxalate:creatinine ratio in the investigation of primary hyperoxaluria: review of data from a referral centre.

PubMed

Clifford-Mobley, Oliver; Tims, Christopher; Rumsby, Gill

2015-01-01

Urine oxalate measurement is an important investigation in the evaluation of renal stone disease. Primary hyperoxaluria (PH) is a rare inherited metabolic disease characterised by persistently elevated urine oxalate, but the diagnosis may be missed in adults until renal failure has developed. Urine oxalate results were reviewed to compare oxalate:creatinine ratio and oxalate excretion, and to estimate the potential numbers of undiagnosed PH. Urine oxalate results from August 2011 to April 2013 were reviewed. Oxalate excretion and oxalate:creatinine ratio were evaluated for 24 h collections and ratio alone for spot urine samples. Oxalate:creatinine ratio and oxalate excretion were moderately correlated (R=0.63) in 24-h urine collections from patients aged 18 years and above. Sex-related differences were found requiring implementation of male and female reference ranges for oxalate:creatinine ratio. Of samples with both ratio and excretion above the reference range, 7% came from patients with confirmed PH. There were 24 patients with grossly elevated urine oxalate who had not been evaluated for PH. Oxalate:creatinine ratio and oxalate excretion were discordant in many patients, which is likely to be a result of intra-individual variation in creatinine output and imprecision in the collection itself. Some PH patients had urine oxalate within the reference range on occasion, and therefore it is not possible to exclude PH on the finding of a single normal result. A significant number of individuals had urine oxalate results well above the reference range who potentially have undiagnosed PH and are consequently at risk of renal failure. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Hydroxyproline Metabolism and Oxalate Synthesis in Primary Hyperoxaluria.

PubMed

Fargue, Sonia; Milliner, Dawn S; Knight, John; Olson, Julie B; Lowther, W Todd; Holmes, Ross P

2018-06-01

Background Endogenous oxalate synthesis contributes to calcium oxalate stone disease and is markedly increased in the inherited primary hyperoxaluria (PH) disorders. The incomplete knowledge regarding oxalate synthesis complicates discovery of new treatments. Hydroxyproline (Hyp) metabolism results in the formation of oxalate and glycolate. However, the relative contribution of Hyp metabolism to endogenous oxalate and glycolate synthesis is not known. Methods To define this contribution, we performed primed, continuous, intravenous infusions of the stable isotope [ 15 N, 13 C 5 ]-Hyp in nine healthy subjects and 19 individuals with PH and quantified the levels of urinary 13 C 2 -oxalate and 13 C 2 -glycolate formed using ion chromatography coupled to mass detection. Results The total urinary oxalate-to-creatinine ratio during the infusion was 73.1, 70.8, 47.0, and 10.6 mg oxalate/g creatinine in subjects with PH1, PH2, and PH3 and controls, respectively. Hyp metabolism accounted for 12.8, 32.9, and 14.8 mg oxalate/g creatinine in subjects with PH1, PH2, and PH3, respectively, compared with 1.6 mg oxalate/g creatinine in controls. The contribution of Hyp to urinary oxalate was 15% in controls and 18%, 47%, and 33% in subjects with PH1, PH2, and PH3, respectively. The contribution of Hyp to urinary glycolate was 57% in controls, 30% in subjects with PH1, and <13% in subjects with PH2 or PH3. Conclusions Hyp metabolism differs among PH types and is a major source of oxalate synthesis in individuals with PH2 and PH3. In patients with PH1, who have the highest urinary excretion of oxalate, the major sources of oxalate remain to be identified. Copyright © 2018 by the American Society of Nephrology.

Enteric oxalate elimination is induced and oxalate is normalized in a mouse model of primary hyperoxaluria following intestinal colonization with Oxalobacter

PubMed Central

Gjymishka, Altin; Salido, Eduardo C.; Allison, Milton J.; Freel, Robert W.

2011-01-01

Oxalobacter colonization of rat intestine was previously shown to promote enteric oxalate secretion and elimination, leading to significant reductions in urinary oxalate excretion (Hatch et al. Kidney Int 69: 691–698, 2006). The main goal of the present study, using a mouse model of primary hyperoxaluria type 1 (PH1), was to test the hypothesis that colonization of the mouse gut by Oxalobacter formigenes could enhance enteric oxalate secretion and effectively reduce the hyperoxaluria associated with this genetic disease. Wild-type (WT) mice and mice deficient in liver alanine-glyoxylate aminotransferase (Agxt) exhibiting hyperoxalemia and hyperoxaluria were used in these studies. We compared the unidirectional and net fluxes of oxalate across isolated, short-circuited large intestine of artificially colonized and noncolonized mice. In addition, plasma and urinary oxalate was determined. Our results demonstrate that the cecum and distal colon contribute significantly to enteric oxalate excretion in Oxalobacter-colonized Agxt and WT mice. In colonized Agxt mice, urinary oxalate excretion was reduced 50% (to within the normal range observed for WT mice). Moreover, plasma oxalate concentrations in Agxt mice were also normalized (reduced 50%). Colonization of WT mice was also associated with marked (up to 95%) reductions in urinary oxalate excretion. We conclude that segment-specific effects of Oxalobacter on intestinal oxalate transport in the PH1 mouse model are associated with a normalization of plasma oxalate and urinary oxalate excretion in otherwise hyperoxalemic and hyperoxaluric animals. PMID:21163900

Oxalates in oca (New Zealand yam) (Oxalis tuberosa Mol.).

PubMed

Ross, A B; Savage, G P; Martin, R J; Vanhanen, L

1999-12-01

Oca (Oxalis tuberosa Mol.) or New Zealand yam, in common with other members of this genus, contains oxalate, an antinutritive factor. Twelve South American and two New Zealand cultivars of oca were analyzed for total and soluble oxalate contents of the tubers. The range of total oxalate levels was 92-221 mg/100 g of fresh weight. Levels of soluble and total oxalate extracted from the tubers were not significantly different, suggesting that no calcium oxalate is formed in the tubers. The oxalate concentrations obtained in this study for oca suggest that previously reported values are too low and that oca is a moderately high oxalate-containing food. This is the first report of a tuber crop containing moderate to high levels of soluble oxalates in the tubers and no insoluble oxalates.

Isolation of oxalic acid tolerating fungi and decipherization of its potential to control Sclerotinia sclerotiorum through oxalate oxidase like protein.

PubMed

Yadav, Shivani; Srivastava, Alok K; Singh, Dhanajay P; Arora, Dilip K

2012-11-01

Oxalic acid plays major role in the pathogenesis by Sclerotinia sclerotiorum; it lowers the pH of nearby environment and creates the favorable condition for the infection. In this study we examined the degradation of oxalic acid through oxalate oxidase and biocontrol of Sclerotinia sclerotiorum. A survey was conducted to collect the rhizospheric soil samples from Indo-Gangetic Plains of India to isolate the efficient fungal strains able to tolerate oxalic acid. A total of 120 fungal strains were isolated from root adhering soils of different vegetable crops. Out of 120 strains a total of 80 isolates were able to grow at 10 mM of oxalic acid whereas only 15 isolates were grow at 50 mM of oxalic acid concentration. Then we examined the antagonistic activity of the 15 isolates against Sclerotinia sclerotiorum. These strains potentially inhibit the growth of the test pathogen. A total of three potential strains and two standard cultures of fungi were tested for the oxalate oxidase activity. Strains S7 showed the maximum degradation of oxalic acid (23 %) after 60 min of incubation with fungal extract having oxalate oxidase activity. Microscopic observation and ITS (internally transcribed spacers) sequencing categorized the potential fungal strains into the Aspergillus, Fusarium and Trichoderma. Trichoderma sp. are well studied biocontrol agent and interestingly we also found the oxalate oxidase type activity in these strains which further strengthens the potentiality of these biocontrol agents.

OXALATE DEPOSITION ON ASBESTOS BODIES

EPA Science Inventory

The clinical and histopathologic findings in three patients with a deposition of calcium oxalate crystals on ferruginous bodies after occupational exposure to asbestos are provided. In addition, we test the hypothesis that this oxalate can be generated through a nonenzymatic o...

Probiotics and Other Key Determinants of Dietary Oxalate Absorption1

PubMed Central

Liebman, Michael; Al-Wahsh, Ismail A.

2011-01-01

Oxalate is a common component of many foods of plant origin, including nuts, fruits, vegetables, grains, and legumes, and is typically present as a salt of oxalic acid. Because virtually all absorbed oxalic acid is excreted in the urine and hyperoxaluria is known to be a considerable risk factor for urolithiasis, it is important to understand the factors that have the potential to alter the efficiency of oxalate absorption. Oxalate bioavailability, a term that has been used to refer to that portion of food-derived oxalate that is absorbed from the gastrointestinal tract (GIT), is estimated to range from 2 to 15% for different foods. Oxalate bioavailability appears to be decreased by concomitant food ingestion due to interactions between oxalate and coingested food components that likely result in less oxalic acid remaining in a soluble form. There is a lack of consensus in the literature as to whether efficiency of oxalate absorption is dependent on the proportion of total dietary oxalate that is in a soluble form. However, studies that directly compared foods of varying soluble oxalate contents have generally supported the proposition that the amount of soluble oxalate in food is an important determinant of oxalate bioavailability. Oxalate degradation by oxalate-degrading bacteria within the GIT is another key factor that could affect oxalate absorption and degree of oxaluria. Studies that have assessed the efficacy of oral ingestion of probiotics that provide bacteria with oxalate-degrading capacity have led to promising but generally mixed results, and this remains a fertile area for future studies. PMID:22332057

Toxic and signalling effects of oxalic acid

PubMed Central

Lehner, Arnaud; Meimoun, Patrice; Errakhi, Rafik; Madiona, Karine; Barakate, Mustapha

2008-01-01

Oxalic acid is thought to be a key factor of the early pathogenic stage in a wide range of necrotrophic fungi. We have recently published that oxalic acid induces Programmed Cell Death (PCD) in Arabidopsis thaliana cells. This cell death results from an early anionic efflux which is a prerequisite for the synthesis of ethylene and the PCD. Complementary experiments have been carried out by using seedlings of A. thaliana. The effects of millimolar concentrations of oxalic acid were analysed on A. thaliana seedlings. A treatment with a 3 mM oxalic acid solution does not alter the development of the plants but induces the transcription of defence related genes which are anion channel dependant. Moreover, our results suggest that a pre-treatment of the seedlings with oxalic acid is able to confer the resistance of A. thaliana against Sclerotium rolfsii. Regarding our results, we suggest that oxalic acid plays two distinct roles, depending on the concentration: a high concentration of oxalic acid induces a large PCD and then contribute to the progression of the fungi. However, at low concentration it is able to induce the establishment of a resistance of the plant against the fungi. PMID:19704845

Asymmetric Catalysis with bis(hydroxyphenyl)diamides/rare-earth metal complexes.

PubMed

Kumagai, Naoya; Shibasaki, Masakatsu

2013-01-02

A series of asymmetric catalysts composed of conformationally flexible amide-based chiral ligands and rare-earth metals was developed for proton-transfer catalysis. These ligands derived from amino acids provide an intriguing chiral platform for the formation of asymmetric catalysts upon complexation with rare-earth metals. The scope of this arsenal of catalysts was further broadened by the development of heterobimetallic catalytic systems. The cooperative function of hydrogen bonding and metal coordination resulted in intriguing substrate specificity and stereocontrol, and the dynamic nature of the catalysts led to a switch of their function. Herein, we summarize our recent exploration of this class of catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microorganisms and calcium oxalate stone disease.

PubMed

Goldfarb, David S

2004-01-01

Microorganisms may have a role in the pathogenesis and prevention of kidney stones. The subjects of this review include nanobacteria, Oxalobacter formigenes, and lactic acid bacteria. Not reviewed here is the well-described role of infections of the urinary tract with Proteus species and other urease-producing organisms associated with struvite stone formation. Nanobacteria have been proposed to be very small (0.08-0.5 nm), ubiquitous organisms that could play a role in stone formation. The theory is that nanobacteria can nucleate carbonate apatite on their surfaces and thereby provide the nidus for stone formation. However, their existence remains uncertain and many investigators are openly skeptical. Recent investigations suggest that they are artifacts, and not actually living organisms, but their proponents continue to study them. O. formigenes is an obligate anaerobe which may be important in the prevention of stone formation. Its sole substrate for generation of ATP is oxalate. It may thereby metabolize its human host's dietary oxalate and diminish intestinal absorption and subsequent urinary excretion of oxalate. There is evidence that the organism's absence, perhaps sometimes due to courses of antibiotics, may be a cause of hyperoxaluria and stone formation. In early investigations, patients not colonized with the organism can be recolonized. Urinary oxalate can be diminished by accompanying an oxalate-containing meal with the organism. One study demonstrated that a preparation of lactic acid bacteria successfully reduced urinary oxalate excretion in 6 patients with calcium oxalate stones and hyperoxaluria. The mechanism of this effect is uncertain since these bacteria lacked the gene possessed by O. formigenes which codes for that organism's oxalate uptake mechanism. The author is currently completing a small randomized controlled clinical trial with this preparation in calcium stone-forming patients with idiopathic hyperoxaluria. Copyright (c) 2004 S

Rare earth-transition metal scrap treatment method

DOEpatents

Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.; Lincoln, Lanny P.

1992-02-11

Rare earth-transition metal (e.g. iron) scrap (e.g. Nd-Fe-B scrap) is melted to reduce the levels of tramp oxygen and nitrogen impurities therein. The tramp impurities are reduced in the melt by virtue of the reaction of the tramp impurities and the rare earth to form dross on the melt. The purified melt is separated from the dross for reuse. The oxygen and nitrogen of the melt are reduced to levels acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets.

Rare earth-transition metal scrap treatment method

DOEpatents

Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.; Lincoln, L.P.

1992-02-11

Rare earth-transition metal (e.g. iron) scrap (e.g. Nd-Fe-B scrap) is melted to reduce the levels of tramp oxygen and nitrogen impurities therein. The tramp impurities are reduced in the melt by virtue of the reaction of the tramp impurities and the rare earth to form dross on the melt. The purified melt is separated from the dross for reuse. The oxygen and nitrogen of the melt are reduced to levels acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. 3 figs.

Pathology and Epidemiology of Oxalate Nephrosis in Cheetahs.

PubMed

Mitchell, Emily P; Church, Molly E; Nemser, Sarah M; Yakes, Betsy Jean; Evans, Eric R; Reimschuessel, Renate; Lemberger, Karin; Thompson, Peter N; Terio, Karen A

2017-11-01

To investigate cases of acute oxalate nephrosis without evidence of ethylene glycol exposure, archived data and tissues from cheetahs ( Acinonyx jubatus) from North America ( n = 297), southern Africa ( n = 257), and France ( n = 40) were evaluated. Renal and gastrointestinal tract lesions were characterized in a subset of animals with ( n = 100) and without ( n = 165) oxalate crystals at death. Crystals were confirmed as calcium oxalate by Raman spectroscopy in 45 of 47 cheetahs tested. Crystals were present in cheetahs from 3.7 months to 15.9 years old. Cheetahs younger than 1.5 years were less likely to have oxalates than older cheetahs ( P = .034), but young cheetahs with oxalates had more oxalate crystals than older cheetahs ( P < .001). Cheetahs with oxalate crystals were more likely to have renal amyloidosis, interstitial nephritis, or colitis and less likely to have glomerular loop thickening or gastritis than those without oxalates. Crystal number was positively associated with renal tubular necrosis ( P ≤ .001), regeneration ( P = .015), and casts ( P ≤ .001) but inversely associated with glomerulosclerosis, renal amyloidosis, and interstitial nephritis. Crystal number was unrelated to the presence or absence of colitis and was lower in southern African than American and European animals ( P = .01). This study found no evidence that coexisting chronic renal disease (amyloidosis, interstitial nephritis, or glomerulosclerosis), veno-occlusive disease, gastritis, or enterocolitis contributed significantly to oxalate nephrosis. Oxalate-related renal disease should be considered as a potential cause of acute renal failure, especially in young captive cheetahs. The role of location, diet, stress, and genetic predisposition in the pathogenesis of oxalate nephrosis in cheetahs warrants further study.

Mechanistic Insight into Caffeine-Oxalic Cocrystal Dissociation in Formulations: Role of Excipients.

PubMed

Duggirala, Naga Kiran; Vyas, Amber; Krzyzaniak, Joseph F; Arora, Kapildev K; Suryanarayanan, Raj

2017-11-06

Caffeine-oxalic acid cocrystal, widely reported to be stable under high humidity, dissociated in the presence of numerous pharmaceutical excipients. In cocrystal-excipient binary systems, the water mediated dissociation reaction occurred under pharmaceutically relevant storage conditions. Powder X-ray diffractometry was used to identify the dissociated products obtained as a consequence of coformer-excipient interaction. The proposed cocrystal dissociation mechanism involved water sorption, dissolution of cocrystal and excipient in the sorbed water, proton transfer from oxalic acid to the excipient, and formation of metal salts and caffeine hydrate. In compressed tablets with magnesium stearate, the cocrystal dissociation was readily discerned from the appearance of peaks attributable to caffeine hydrate and stearic acid. Neutral excipients provide an avenue to circumvent the risk of water mediated cocrystal dissociation.

Electrochemical synthesis and characterization of zinc oxalate nanoparticles

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

Shamsipur, Mojtaba, E-mail: mshamsipur@yahoo.com; Roushani, Mahmoud; Department of Chemistry, Ilam University, Ilam

2013-03-15

Highlights: ► Synthesis of zinc oxalate nanoparticles via electrolysis of a zinc plate anode in sodium oxalate solutions. ► Design of a Taguchi orthogonal array to identify the optimal experimental conditions. ► Controlling the size and shape of particles via applied voltage and oxalate concentration. ► Characterization of zinc oxalate nanoparticles by SEM, UV–vis, FT-IR and TG–DTA. - Abstract: A rapid, clean and simple electrodeposition method was designed for the synthesis of zinc oxalate nanoparticles. Zinc oxalate nanoparticles in different size and shapes were electrodeposited by electrolysis of a zinc plate anode in sodium oxalate aqueous solutions. It was foundmore » that the size and shape of the product could be tuned by electrolysis voltage, oxalate ion concentration, and stirring rate of electrolyte solution. A Taguchi orthogonal array design was designed to identify the optimal experimental conditions. The morphological characterization of the product was carried out by scanning electron microscopy. UV–vis and FT-IR spectroscopies were also used to characterize the electrodeposited nanoparticles. The TG–DTA studies of the nanoparticles indicated that the main thermal degradation occurs in two steps over a temperature range of 350–430 °C. In contrast to the existing methods, the present study describes a process which can be easily scaled up for the production of nano-sized zinc oxalate powder.« less

Laboratory study of the effect of oxalic acid on the cloud condensation nuclei activity of mineral dust aerosol

NASA Astrophysics Data System (ADS)

Gierlus, Kelly M.; Laskina, Olga; Abernathy, Tricia L.; Grassian, Vicki H.

2012-01-01

Dicarboxylic acids, which make up a significant portion of the atmospheric organic aerosol, are emitted directly through biomass burning as well as produced through the oxidation of volatile organic compounds. Oxalic acid, the most abundant of the dicarboxylic acids, has been shown by recent field studies to be present in mineral dust aerosol particles. The presence of these internally mixed organic compounds can alter the water absorption and cloud condensation nuclei (CCN) abilities of mineral particles in the Earth's atmosphere. The University of Iowa's Multi-Analysis Aerosol Reactor System ( MAARS) was used to measure the CCN activity of internally mixed particles that were generated from a mixture of either calcite or polystyrene latex spheres (PSLs) in an aqueous solution of oxalic acid. Although PSL is not a mineral dust component, it is used here as a non-reactive, insoluble particle. CCN measurements indicate that the internally mixed oxalate/calcite particles showed nearly identical CCN activity compared to the original calcite particles whereas oxalic acid/PSL internally mixed particles showed much greater CCN activity compared to PSL particles alone. This difference is due to the reaction of calcite with oxalic acid, which produces a relatively insoluble calcium oxalate coating on the particle surface and not a soluble coating as it does on the PSL particle. Our results suggest that atmospheric processing of mineral dust aerosol through heterogeneous processes will likely depend on the mineralogy and the specific chemistry involved. Increase in the CCN activity by incorporation of oxalic acid are only expected for unreactive insoluble dust particles that form a soluble coating.

Catalysts Based on Earth-Abundant Metals for Visible Light-Driven Water Oxidation Reaction.

PubMed

Lin, Junqi; Han, Qing; Ding, Yong

2018-06-04

Exploration of water oxidation catalyst (WOC) with excellent performance is the key for the overall water splitting reaction, which is a feasible strategy to convert solar energy to chemical energy. Although some compounds composed of noble metals, mainly Ru and Ir, have been reported to catalyze water oxidation with high efficiency, catalysts based on low-cost and earth-abundant transition metals are essential for realizing economical and large-scale light-driven water splitting. Various WOCs containing earth-abundant metals (mainly Mn, Fe, Co, Ni, Cu) have been utilized for visible light-driven water oxidation in recent years. In this Personal Account, we summarize our recent developments in WOCs based on earth-abundant transition metals including polyoxometalates (POMs), metal oxides or bimetal oxides, and metal complexes containing multidentate ligand scaffolds for visible light-driven water oxidation reaction. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Total and soluble oxalate content of some Indian spices.

PubMed

Ghosh Das, Sumana; Savage, G P

2012-06-01

Spices, such as cinnamon, cloves, cardamom, garlic, ginger, cumin, coriander and turmeric are used all over the world as flavouring and colouring ingredients in Indian foods. Previous studies have shown that spices contain variable amounts of total oxalates but there are few reports of soluble oxalate contents. In this study, the total, soluble and insoluble oxalate contents of ten different spices commonly used in Indian cuisine were measured. Total oxalate content ranged from 194 (nutmeg) to 4,014 (green cardamom) mg/100 g DM, while the soluble oxalate contents ranged from 41 (nutmeg) to 3,977 (green cardamom) mg/100 g DM. Overall, the percentage of soluble oxalate content of the spices ranged from 4.7 to 99.1% of the total oxalate content which suggests that some spices present no risk to people liable to kidney stone formation, while other spices can supply significant amounts of soluble oxalates and therefore should be used in moderation.

Atmospheric production of oxalic acid/oxalate and nitric acid/nitrate in the Tampa Bay airshed: Parallel pathways

NASA Astrophysics Data System (ADS)

Martinelango, P. Kalyani; Dasgupta, Purnendu K.; Al-Horr, Rida S.

Oxalic acid is the dominant dicarboxylic acid (DCA), and it constitutes up to 50% of total atmospheric DCAs, especially in non-urban and marine atmospheres. A significant amount of particulate H 2Ox/oxalate (Ox) occurred in the coarse particle fraction of a dichotomous sampler, the ratio of oxalate concentrations in the PM 10 to PM 2.5 fractions ranged from 1 to 2, with mean±sd being 1.4±0.2. These results suggest that oxalate does not solely originate in the gas phase and condense into particles. Gaseous H 2Ox concentrations are much lower than particulate Ox concentrations and are well correlated with HNO 3, HCHO, and O 3, supporting a photochemical origin. Of special relevance to the Bay Region Atmospheric Chemistry Experiment (BRACE) is the extent of nitrogen deposition in the Tampa Bay estuary. Hydroxyl radical is primarily responsible for the conversion of NO 2 to HNO 3, the latter being much more easily deposited. Hydroxyl radical is also responsible for the aqueous phase formation of oxalic acid from alkenes. Hence, we propose that an estimate of rad OH can be obtained from H 2Ox/Ox production rate and we accordingly show that the product of total oxalate concentration and NO 2 concentration approximately predicts the total nitrate concentration during the same period.

Oxalobacter formigenes Colonization and Oxalate Dynamics in a Mouse Model

PubMed Central

Li, Xingsheng; Ellis, Melissa L.

2015-01-01

Animal and human studies have provided compelling evidence that colonization of the intestine with Oxalobacter formigenes reduces urinary oxalate excretion and lowers the risk of forming calcium oxalate kidney stones. The mechanism providing protection appears to be related to the unique ability of O. formigenes to rely on oxalate as a major source of carbon and energy for growth. However, much is not known about the factors that influence colonization and host-bacterium interactions. We have colonized mice with O. formigenes OxCC13 and systematically investigated the impacts of diets with different levels of calcium and oxalate on O. formigenes intestinal densities and urinary and intestinal oxalate levels. Measurement of intestinal oxalate levels in mice colonized or not colonized with O. formigenes demonstrated the highly efficient degradation of soluble oxalate by O. formigenes relative to other microbiota. The ratio of calcium to oxalate in diets was important in determining colonization densities and conditions where urinary oxalate and fecal oxalate excretion were modified, and the results were consistent with those from studies we have performed with colonized and noncolonized humans. The use of low-oxalate purified diets showed that 80% of animals retained O. formigenes colonization after a 1-week dietary oxalate deprivation. Animals not colonized with O. formigenes excreted two times more oxalate in feces than they had ingested. This nondietary source of oxalate may play an important role in the survival of O. formigenes during periods of dietary oxalate deprivation. These studies suggest that the mouse will be a useful model to further characterize interactions between O. formigenes and the host and factors that impact colonization. PMID:25979889

Process for preparing higher oxides of the alkali and alkaline earth metals

NASA Technical Reports Server (NTRS)

Sadhukhan, P.; Bell, A. (Inventor)

1978-01-01

High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

Pseudomonas fluorescens ATCC 13525 Containing an Artificial Oxalate Operon and Vitreoscilla Hemoglobin Secretes Oxalic Acid and Solubilizes Rock Phosphate in Acidic Alfisols

PubMed Central

Archana, G.; Naresh Kumar, G.

2014-01-01

Oxalate secretion was achieved in Pseudomonas fluorescens ATCC 13525 by incorporation of genes encoding Aspergillus niger oxaloacetate acetyl hydrolase (oah), Fomitopsis plaustris oxalate transporter (FpOAR) and Vitreoscilla hemoglobin (vgb) in various combinations. Pf (pKCN2) transformant containing oah alone accumulated 19 mM oxalic acid intracellularly but secreted 1.2 mM. However, in the presence of an artificial oxalate operon containing oah and FpOAR genes in plasmid pKCN4, Pf (pKCN4) secreted 13.6 mM oxalate in the medium while 3.6 mM remained inside. This transformant solubilized 509 μM of phosphorus from rock phosphate in alfisol which is 4.5 fold higher than the Pf (pKCN2) transformant. Genomic integrants of P. fluorescens (Pf int1 and Pf int2) containing artificial oxalate operon (plac-FpOAR-oah) and artificial oxalate gene cluster (plac-FpOAR-oah, vgb, egfp) secreted 4.8 mM and 5.4 mM oxalic acid, released 329 μM and 351 μM P, respectively, in alfisol. The integrants showed enhanced root colonization, improved growth and increased P content of Vigna radiata plants. This study demonstrates oxalic acid secretion in P. fluorescens by incorporation of an artificial operon constituted of genes for oxalate synthesis and transport, which imparts mineral phosphate solubilizing ability to the organism leading to enhanced growth and P content of V. radiata in alfisol soil. PMID:24705024

Calcium Oxalate Urolithiasis: A Case of Missing Microbes?

PubMed

Batagello, Carlos Alfredo; Monga, Manoj; Miller, Aaron W

2018-05-29

Urinary stone disease (USD) has known associations with the gut microbiota. Approximately 80% of kidney stones contain oxalate as a primary constituent and diverse oxalate-degrading bacteria exist within the human gut that may protect against USD. While bacteriotherapy represents a promising strategy to eliminate oxalate and reduce the risk of USD, oxalate-degrading probiotics have had limited success. To identify limitations of oxalate-degrading probiotics and refine development of bacteriotherapies to prevent USD, we review the literature associated with the gut microbiota and USD. A literature search was performed to identify publications that examine the role of oxalate-degrading bacteria or the whole gut microbiota in oxalate metabolism and the pathophysiology of USD. We conducted a meta-analysis of studies that examined the association of the whole gut microbiota with USD. In addition, we evaluated the gut microbiota of healthy individuals and those with co-morbidities related to USD using publically available data from the American Gut Project (AGP). Studies on O. formigenes reveal that colonization by this species is not a good predictor of USD risk nor urinary oxalate excretion. The species of oxalate-degrading bacteria used in probiotics and duration of administration does not impact efficacy or persistence. Studies focused on the whole gut microbiota reveal broad shifts in the gut microbiota associated with USD and a diverse microbial network is associated with oxalate metabolism. AGP data analysis demonstrated a strong overlap in microbial genera depleted in diseased individuals among USD and co-morbidities. The associations between the gut microbiota and USD extend beyond individual functional microbial species. Common shifts in the gut microbiota may facilitate the onset of USD and/or co-morbidities. The successful development of bacteriotherapies to inhibit USD will need to incorporate strategies that target a broad diversity of bacteria rather than

Oxalate Content of Taro Leaves Grown in Central Vietnam.

PubMed

Du Thanh, Hang; Phan Vu, Hai; Vu Van, Hai; Le Duc, Ngoan; Le Minh, Tuan; Savage, Geoffrey

2017-01-01

Leaves were harvested from four different cultivars of Colocasia esculenta and three cultivars of Alocasia odora that were growing on nine different farms in central Vietnam. The total, soluble and insoluble oxalate contents of the leaves were extracted and measured using HPLC chromatography. Total calcium determinations were also carried out on the same samples. The total oxalate content of the leaves ranged from 433.8 to 856.1 mg/100 g wet matter (WM) while the soluble oxalate ranged from 147.8 to 339.7 mg/100 g WM. The proportion of soluble oxalate ranged from 28% to 41% (overall mean 35%) of the total oxalate content of the leaves. The equivalent insoluble oxalate proportion ranged from 59% to 72% of the total (overall mean 65%). There was little difference between the Colocasia esculenta and Alocasia odora taro cultivars, although the total oxalate content was significantly higher in Alocasia odora cultivars. The overall mean total calcium content was 279.5 mg/100 WM and the percentage of insoluble calcium bound as calcium oxalate ranged from 31.7% to 57.3% of the total calcium content (overall mean 47.1%). The oxalate content in taro leaves is a major factor to consider when different cultivars of taro are recommended for human or animal consumption.

Loss of Cystic Fibrosis Transmembrane Regulator Impairs Intestinal Oxalate Secretion.

PubMed

Knauf, Felix; Thomson, Robert B; Heneghan, John F; Jiang, Zhirong; Adebamiro, Adedotun; Thomson, Claire L; Barone, Christina; Asplin, John R; Egan, Marie E; Alper, Seth L; Aronson, Peter S

2017-01-01

Patients with cystic fibrosis have an increased incidence of hyperoxaluria and calcium oxalate nephrolithiasis. Net intestinal absorption of dietary oxalate results from passive paracellular oxalate absorption as modified by oxalate back secretion mediated by the SLC26A6 oxalate transporter. We used mice deficient in the cystic fibrosis transmembrane conductance regulator gene (Cftr) to test the hypothesis that SLC26A6-mediated oxalate secretion is defective in cystic fibrosis. We mounted isolated intestinal tissue from C57BL/6 (wild-type) and Cftr -/- mice in Ussing chambers and measured transcellular secretion of [ 14 C]oxalate. Intestinal tissue isolated from Cftr -/- mice exhibited significantly less transcellular oxalate secretion than intestinal tissue of wild-type mice. However, glucose absorption, another representative intestinal transport process, did not differ in Cftr -/- tissue. Compared with wild-type mice, Cftr -/- mice showed reduced expression of SLC26A6 in duodenum by immunofluorescence and Western blot analysis. Furthermore, coexpression of CFTR stimulated SLC26A6-mediated Cl - -oxalate exchange in Xenopus oocytes. In association with the profound defect in intestinal oxalate secretion, Cftr -/- mice had serum and urine oxalate levels 2.5-fold greater than those of wild-type mice. We conclude that defective intestinal oxalate secretion mediated by SLC26A6 may contribute to the hyperoxaluria observed in this mouse model of cystic fibrosis. Future studies are needed to address whether similar mechanisms contribute to the increased risk for calcium oxalate stone formation observed in patients with cystic fibrosis. Copyright © 2016 by the American Society of Nephrology.

The influence of oxalate-promoted growth of saponite and talc crystals

USGS Publications Warehouse

Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D.; Sears, S. Kelly; Hesse, Reinhard; Vali, Hojatollah

2013-01-01

The intercalating growth of new silicate layers or metal hydroxide layers in the interlayer space of other clay minerals is known from various mixed-layer clay minerals such as illite-smectite (I-S), chlorite-vermiculite, and mica-vermiculite. In a recent study, the present authors proposed that smectite-group minerals can be synthesized from solution as new 2:1 silicate layers within the low-charge interlayers of rectorite. That study showed how oxalate catalyzes the crystallization of saponite from a silicate gel at low temperatures (60ºC) and ambient pressure. As an extension of this work the aim of the present study was to test the claim that new 2:1 silicate layers can be synthesized as new intercalating layers in the low-charge interlayers of rectorite and whether oxalate could promote such an intercalation synthesis. Two experiments were conducted at 60ºC and atmospheric pressure. First, disodium oxalate solution was added to a suspension of rectorite in order to investigate the effects that oxalate anions have on the structure of rectorite. In a second experiment, silicate gel of saponitic composition (calculated interlayer charge −0.33 eq/O10(OH)2) was mixed with a suspension of rectorite and incubated in disodium oxalate solution. The synthesis products were extracted after 3 months and analyzed by X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The treatment of ultrathin sections with octadecylammonium (nC = 18) cations revealed the presence of 2:1 layer silicates with different interlayer charges that grew from the silicate gel. The oxalate-promoted nucleation of saponite and talc crystallites on the rectorite led to the alteration and ultimately to the destruction of the rectorite structure. The change was documented in HRTEM lattice-fringe images. The crystallization of new 2:1 layer silicates also occurred within the expandable interlayers of rectorite but not as new 2:1 silicate layers parallel to the previous 2

Oxalate Content of the Herb Good-King-Henry, Blitum Bonus-Henricus

PubMed Central

Li, Wanying; Savage, Geoffrey P.

2015-01-01

The total, soluble and insoluble oxalate contents of the leaves, stems and buds of Good-King-Henry (Blitum Bonus-Henricus) were extracted and measured using HPLC chromatography. The large, mature leaves contained 42% more total oxalate than in the small leaves and the soluble oxalate content of the large leaves was 33% higher than the smaller leaves. Cooking the mixed leaves, stems and buds in boiling water for two minutes significantly (p < 0.05) reduced the total oxalate when compared to the raw plant parts. Pesto sauce made from mixed leaves contained 257 mg total oxalate/100 g fresh weight; this was largely made up of insoluble oxalates (85% of the total oxalate content). Soup made from mixed leaves contained lower levels of total oxalates (44.26 ± 0.49 mg total oxalate/100 g fresh weight) and insoluble oxalate made up 49% of the oxalate contents. The levels of oxalates in the Good-King-Henry leaves were high, suggesting that the leaves should be consumed occasionally as a delicacy because of their unique taste rather than as a significant part of the diet. However, the products made from Good-King-Henry leaves indicated that larger amounts could be consumed as the oxalate levels were reduced by dilution and processing. PMID:28231194

Urinary oxalate to creatinine ratios in healthy Turkish schoolchildren.

PubMed

Dursun, Ismail; Çelik, İlknur; Poyrazoglu, Hakan M; Köse, Kader; Tanrıkulu, Esen; Sahin, Habibe; Yılmaz, Kenan; Öztürk, Ahmet; Yel, Sibel; Gündüz, Zübeyde; Düşünsel, Ruhan

2017-11-01

we aimed to establish reference values for urinary oxalate to creatinine ratios in healthy children aged 6-15 years and to investigate the relationship between their nutritional habits and oxalate excretion. Random urine specimens from 953 healthy children aged 6-15 years were obtained and analyzed for oxalate and creatinine. Additionally, a 24-h dietary recall form was prepared and given to them. The ingredient composition of the diet was calculated. The children were divided into three groups according to age: Group I (69 years, n = 353), Group II (10-12 years, n = 335), and Group III (13-15 years, n = 265). The 95th percentile of the oxalate to creatinine ratio for subjects aged 6-9, 10-12, and 13-15 years were 0.048, 0.042, and 0.042 mg/mg, respectively. The oxalate to creatinine ratio was significantly higher in Group 1 than in Group 2 and Group 3. Urinary oxalate excretion was positively correlated with increased protein intake and negatively correlated with age. A significant positive correlation was determined between urinary oxalate excretion and the proline, serine, protein, and glycine content of diet. Dietary proline intake showed a positive correlation with the urine oxalate to creatinine ratio and was found to be an independent predictor for urinary oxalate. These data lend support to the idea that every country should have its own normal reference values to determine the underlying metabolic risk factor for kidney stone disease since regional variation in the dietary intake of proteins and other nutrients can affect normal urinary excretion of oxalate.

Oxalate quantification in hemodialysate to assess dialysis adequacy for primary hyperoxaluria

PubMed Central

Tang, Xiaojing; Voskoboev, Nikolay V.; Wannarka, Stacie L.; Olson, Julie B.; Milliner, Dawn S.; Lieske, John C.

2015-01-01

Background Patients with primary hyperoxaluria (PH) overproduce oxalate which is eliminated via the kidneys. If end stage kidney disease develops they are at high risk for systemic oxalosis, unless adequate oxalate is removed during hemodialysis to equal or exceed ongoing oxalate production. The purpose of this study was to validate a method to measure oxalate removal in this unique group of dialysis patients. Methods Fourteen stable patients with a confirmed diagnosis of PH on hemodialysis were included in the study. Oxalate was measured serially in hemodialysate and plasma samples in order to calculate rates of oxalate removal. Hemodialysis regimens were adjusted according to a given patient's historical oxalate production, amount of oxalate removal at dialysis, residual renal clearance of oxalate, and plasma oxalate levels. Results After a typical session of hemodialysis, plasma oxalate was reduced by 78.4±7.7%. Eight patients performed hemodialysis 6 times a week, two patients 5 times a week and three patients 3 times a week. Combined oxalate removal by hemodialysis and the kidneys was sufficient to match or exceed endogenous oxalate production. After a median period of 9 months, pre-dialysis plasma oxalate was significantly lower than initially (75.1±33.4 mmol/L vs. 54.8±46.6 mmol/L, P=0.02). Conclusion This methodology can be used to individualize the dialysis prescription of PH patients to prevent oxalosis during the time they are maintained on hemodialysis, and to reduce risk of oxalate injury to a transplanted kidney. PMID:24776840

Isolation and characterizations of oxalate-binding proteins in the kidney

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

Roop-ngam, Piyachat; Chaiyarit, Sakdithep; Pongsakul, Nutkridta

Highlights: Black-Right-Pointing-Pointer The first large-scale characterizations of oxalate-binding kidney proteins. Black-Right-Pointing-Pointer The recently developed oxalate-conjugated EAH Sepharose 4B beads were applied. Black-Right-Pointing-Pointer 38 forms of 26 unique oxalate-binding kidney proteins were identified. Black-Right-Pointing-Pointer 25/26 (96%) of identified proteins had 'L-x(3,5)-R-x(2)-[AGILPV]' domain. -- Abstract: Oxalate-binding proteins are thought to serve as potential modulators of kidney stone formation. However, only few oxalate-binding proteins have been identified from previous studies. Our present study, therefore, aimed for large-scale identification of oxalate-binding proteins in porcine kidney using an oxalate-affinity column containing oxalate-conjugated EAH Sepharose 4B beads for purification followed by two-dimensional gel electrophoresis (2-DE) tomore » resolve the recovered proteins. Comparing with those obtained from the controlled column containing uncoupled EAH-Sepharose 4B (to subtract the background of non-specific bindings), a total of 38 protein spots were defined as oxalate-binding proteins. These protein spots were successfully identified by quadrupole time-of-flight mass spectrometry (MS) and/or tandem MS (MS/MS) as 26 unique proteins, including several nuclear proteins, mitochondrial proteins, oxidative stress regulatory proteins, metabolic enzymes and others. Identification of oxalate-binding domain using the PRATT tool revealed 'L-x(3,5)-R-x(2)-[AGILPV]' as a functional domain responsible for oxalate-binding in 25 of 26 (96%) unique identified proteins. We report herein, for the first time, large-scale identification and characterizations of oxalate-binding proteins in the kidney. The presence of positively charged arginine residue in the middle of this functional domain suggested its significance for binding to the negatively charged oxalate. These data will enhance future stone research, particularly on stone

When VSEPR Fails: Experimental and Theoretical Investigations of the Behavior of Alkaline-Earth-Metal Acetylides

PubMed Central

Guino-o, Marites A.; Alexander, Jacob S.; McKee, Michael L.; Hope, Håkon; Englich, Ulrich B.

2014-01-01

The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline-earth-metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication that reported unusual geometry for a family of triphenylsilyl-substituted alkaline-earth-metal acetylides, we herein present our studies on an expanded family of target derivatives, providing experimental and theoretical data to offer new insights into the intensively debated theme of structural chemistry in heavy alkaline-earth-metal chemistry. PMID:19844925

Sequential electrokinetic treatment and oxalic acid extraction for the removal of Cu, Cr and As from wood.

PubMed

Isosaari, Pirjo; Marjavaara, Pieti; Lehmus, Eila

2010-10-15

Removal of Cu, Cr and As from utility poles treated with chromated copper arsenate (CCA) was investigated using different one- to three-step combinations of oxalic acid extraction and electrokinetic treatment. The experiments were carried out at room temperature, using 0.8% oxalic acid and 30 V (200 V/m) of direct current (DC) or alternating current in combination (DC/AC). Six-hour extraction removed only 15%, 11% and 28% and 7-day electrokinetic treatment 57%, 0% and 17% of Cu, Cr and As from wood chips, respectively. The best combination for all the metals was a three-step process consisting of pre-extraction, electrokinetics and post-extraction steps, yielding removals of 67% for Cu, 64% for Cr and 81% for As. Oxalic acid extraction prior to electrokinetic treatment was deleterious to further removal of Cu, but it was necessary for Cr and As removal. Chemical equilibrium modelling was used to explain the differences in the behaviour of Cu, Cr and As. Due to the dissimilar nature of these metals, it appeared that even more process sequences and/or stricter control of the process conditions would be needed to obtain the >99% removals required for safe recycling of the purified wood material. 2010 Elsevier B.V. All rights reserved.

Urinary oxalate to creatinine ratios in healthy Turkish schoolchildren

PubMed Central

Dursun, Ismail; Çelik, İlknur; Poyrazoglu, Hakan M.; Tanrıkulu, Esen; Sahin, Habibe; Yılmaz, Kenan; Öztürk, Ahmet; Yel, Sibel; Gündüz, Zübeyde; Düşünsel, Ruhan

2017-01-01

Abstract Aim: we aimed to establish reference values for urinary oxalate to creatinine ratios in healthy children aged 6–15 years and to investigate the relationship between their nutritional habits and oxalate excretion. Materials and methods: Random urine specimens from 953 healthy children aged 6–15 years were obtained and analyzed for oxalate and creatinine. Additionally, a 24-h dietary recall form was prepared and given to them. The ingredient composition of the diet was calculated. The children were divided into three groups according to age: Group I (69 years, n = 353), Group II (10–12 years, n = 335), and Group III (13–15 years, n = 265). Results: The 95th percentile of the oxalate to creatinine ratio for subjects aged 6–9, 10–12, and 13–15 years were 0.048, 0.042, and 0.042 mg/mg, respectively. The oxalate to creatinine ratio was significantly higher in Group 1 than in Group 2 and Group 3. Urinary oxalate excretion was positively correlated with increased protein intake and negatively correlated with age. A significant positive correlation was determined between urinary oxalate excretion and the proline, serine, protein, and glycine content of diet. Dietary proline intake showed a positive correlation with the urine oxalate to creatinine ratio and was found to be an independent predictor for urinary oxalate. Conclusions: These data lend support to the idea that every country should have its own normal reference values to determine the underlying metabolic risk factor for kidney stone disease since regional variation in the dietary intake of proteins and other nutrients can affect normal urinary excretion of oxalate. PMID:27846788

Oxalate exposure provokes HSP 70 response in LLC-PK1 cells, a line of renal epithelial cells: protective role of HSP 70 against oxalate toxicity.

PubMed

Koul, Sweaty; Huang, Meiyi; Bhat, Sidarth; Maroni, Paul; Meacham, Randall B; Koul, Hari K

2008-02-01

We investigated the effects of oxalate on immediate early genes (IEGs) and stress protein HSP 70, commonly induced genes in response to a variety of stresses. LLC-PK1 cells were exposed to oxalate. Gene transcription and translation were monitored by Northern and Western blot analysis. RNA and DNA synthesis were assessed by [(3)H]-uridine and [(3)H]-thymidine incorporation, respectively. Oxalate exposure selectively increased the levels of mRNA encoding IEGs c-myc and c-jun as well as stress protein HSP 70. While expression of c-myc and c-jun was rapid (within 15 min to 2 h) and transient, HSP 70 expression was delayed (approximately 8 h) and stable. Furthermore, oxalate exposure resulted in delayed induction of generalized transcription by 18 h and reinitiation of the DNA synthesis by 24 h of oxalate exposure. Moreover, we show that prior induction of HSP 70 by mild hypertonic exposure protected the cells from oxalate toxicity. To the best of our knowledge this is the first study to demonstrate rapid IEG response and delayed heat-shock response to oxalate toxicity and protective role of HSP 70 against oxalate toxicity to renal epithelial cells. Oxalate, a metabolic end product, induces IEGs c-myc and c-jun and a delayed HSP 70 expression; While IEG expression may regulate additional genetic responses to oxalate, increased HSP 70 expression would serve an early protective role during oxalate stress.

Application of Freeze-Dried Powders of Genetically Engineered Microbial Strains as Adsorbents for Rare Earth Metal Ions.

PubMed

Moriwaki, Hiroshi; Masuda, Reiko; Yamazaki, Yuki; Horiuchi, Kaoru; Miyashita, Mari; Kasahara, Jun; Tanaka, Tatsuhito; Yamamoto, Hiroki

2016-10-12

The adsorption behaviors of the rare earth metal ions onto freeze-dried powders of genetically engineered microbial strains were compared. Cell powders obtained from four kinds of strains, Bacillus subtilis 168 wild type (WT), lipoteichoic acid-defective (ΔLTA), wall teichoic acid-defective (ΔWTA), and cell wall hydrolases-defective (EFKYOJLp) strains, were used as an adsorbent of the rare earth metal ions at pH 3. The adsorption ability of the rare earth metal ions was in the order of EFKYOJLp > WT > ΔLTA > ΔWTA. The order was the same as the order of the phosphorus quantity of the strains. This result indicates that the main adsorption sites for the ions are the phosphate groups and the teichoic acids, LTA and WTA, that contribute to the adsorption of the rare earth metal ions onto the cell walls. The contribution of WTA was clearly greater than that of LTA. Each microbial powder was added to a solution containing 16 kinds of rare earth metal ions, and the removals (%) of each rare earth metal ion were obtained. The scandium ion showed the highest removal (%), while that of the lanthanum ion was the lowest for all the microbial powders. Differences in the distribution coefficients between the kinds of lanthanide ions by the EFKYOJLp and ΔWTA powders were greater than those of the other strains. Therefore, the EFKYOJLp and ΔWTA powders could be applicable for the selective extraction of the lanthanide ions. The ΔLTA powder coagulated by mixing with a rare earth metal ion, although no sedimentation of the WT or ΔWTA powder with a rare earth metal ion was observed under the same conditions. The EFKYOJLp powder was also coagulated, but its flocculating activity was lower than that of ΔLTA. The ΔLTA and EFKYOJLp powders have a long shape compared to those of the WT or ΔWTA strain. The shapes of the cells will play an important role in the sedimentation of the microbial powders with rare earth metal ions. As the results, three kinds of the genetically

A new approach to study cadmium complexes with oxalic acid in soil solution.

PubMed

Dytrtová, Jana Jaklová; Jakl, Michal; Sestáková, Ivana; Zins, Emilie-Laure; Schröder, Detlef; Navrátil, Tomáš

2011-05-05

This study presents a new analytical approach for the determination of heavy metals complexed to low-molecular-weight-organic acids in soil solutions, which combines the sensitivity of differential pulse anodic stripping voltammetry (DPASV) with the molecular insight gained by electrospray ionization mass spectrometry (ESI-MS). The combination of these analytical methods allows the investigation of such complexes in complex matrixes. On the voltammograms of the soil solutions, in addition to the expected complexes of oxalic acid with cadmium and lead, respectively, also peaks belonging to mixed complexes of cadmium, lead, and oxalic acid (OAH(2)) were observed. In order to verify the possible formation of complexes with OAH(2), aqueous solutions of OAH(2) with traces of Cd(II) were investigated as model systems. Signals corresponding to several distinct molecular complexes between cadmium and oxalic acid were detected in the model solutions using negative-ion ESI-MS, which follow the general formula [Cd(n)(X,Y)((2n+1))](-), where n is the number of cadmium atoms, X=Cl(-), and Y=OAH(-). Some of these complexes were also identified in the ESI mass spectra taken from the soil solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

Transcellular oxalate and Cl− absorption in mouse intestine is mediated by the DRA anion exchanger Slc26a3, and DRA deletion decreases urinary oxalate

PubMed Central

Freel, Robert W.; Whittamore, Jonathan M.

2013-01-01

Active transcellular oxalate transport in the mammalian intestine contributes to the homeostasis of this important lithogenic anion. Several members of the Slc26a gene family of anion exchangers have a measurable oxalate affinity and are expressed along the gut, apically and basolaterally. Mouse Slc26a6 (PAT1) targets to the apical membrane of enterocytes in the small intestine, and its deletion results in net oxalate absorption and hyperoxaluria. Apical exchangers of the Slc26a family that mediate oxalate absorption have not been established, yet the Slc26a3 [downregulated in adenoma (DRA)] protein is a candidate mediator of oxalate uptake. We evaluated the role of DRA in intestinal oxalate and Cl− transport by comparing unidirectional and net ion fluxes across short-circuited segments of small (ileum) and large (cecum and distal colon) intestine from wild-type (WT) and DRA knockout (KO) mice. In WT mice, all segments demonstrated net oxalate and Cl− absorption to varying degrees. In KO mice, however, all segments exhibited net anion secretion, which was consistently, and solely, due to a significant reduction in the absorptive unidirectional fluxes. In KO mice, daily urinary oxalate excretion was reduced 66% compared with that in WT mice, while urinary creatinine excretion was unchanged. We conclude that DRA mediates a predominance of the apical uptake of oxalate and Cl− absorbed in the small and large intestine of mice under short-circuit conditions. The large reductions in urinary oxalate excretion underscore the importance of transcellular intestinal oxalate absorption, in general, and, more specifically, the importance of the DRA exchanger in oxalate homeostasis. PMID:23886857

Environmental Defects And Economic Impact On Global Market Of Rare Earth Metals

NASA Astrophysics Data System (ADS)

Charalampides, G.; Vatalis, K.; Karayannis, V.; Baklavaridis, A.

2016-11-01

Rare earth elements include the 14 lanthanides as well as lanthanium and often yttrium. Actually, most of them are not very rare and occur widely dispersed in a variety of rocks. Rare earth metals are vital to some of the world's faster growing industries: catalysts, Nd-magnets, ceramics, glass, metallurgy, battery alloys, electronics and phosphors. Worldwide, the main countries for distribution of rare earths deposits include China, USA, Russia, Brasil, India, Australia, Greenland and Malaysia. The mining and processing of rare earth metals usually result in significant environmental defects. Many deposits are associated with high concentrations of radioactive elements such as uranium and thorium, which requires separate treatment and disposal. The accumulation of rare earth elements in soils has occurred due to pollution caused by the exploitation of rare earth resources and the wide use of rare earths as fertilizers in agriculture. This accumulation has a toxic effect on the soil microfauna community. However, there are large differences in market prices due to the degree of purity determined by the specifications in the applications. The main focus of this article is to overview Rare Earth Metals’ overall impact on global economy and their environmental defects on soils during processing techniques and as they are used as fertilizers.

Sat1 is dispensable for active oxalate secretion in mouse duodenum

PubMed Central

Ko, Narae; Knauf, Felix; Jiang, Zhirong; Markovich, Daniel

2012-01-01

Mice deficient for the apical membrane oxalate transporter SLC26A6 develop hyperoxalemia, hyperoxaluria, and calcium oxalate stones due to a defect in intestinal oxalate secretion. However, the nature of the basolateral membrane oxalate transport process that operates in series with SLC26A6 to mediate active oxalate secretion in the intestine remains unknown. Sulfate anion transporter-1 (Sat1 or SLC26A1) is a basolateral membrane anion exchanger that mediates intestinal oxalate transport. Moreover, Sat1-deficient mice also have a phenotype of hyperoxalemia, hyperoxaluria, and calcium oxalate stones. We, therefore, tested the role of Sat1 in mouse duodenum, a tissue with Sat1 expression and SLC26A6-dependent oxalate secretion. Although the active secretory flux of oxalate across mouse duodenum was strongly inhibited (>90%) by addition of the disulfonic stilbene DIDS to the basolateral solution, secretion was unaffected by changes in medium concentrations of sulfate and bicarbonate, key substrates for Sat1-mediated anion exchange. Inhibition of intracellular bicarbonate production by acetazolamide and complete removal of bicarbonate from the buffer also produced no change in oxalate secretion. Finally, active oxalate secretion was not reduced in Sat1-null mice. We conclude that a DIDS-sensitive basolateral transporter is involved in mediating oxalate secretion across mouse duodenum, but Sat1 itself is dispensable for this process. PMID:22517357

Theoretical study on the structure and stabilities of molecular clusters of oxalic acid with water.

PubMed

Weber, Kevin H; Morales, Francisco J; Tao, Fu-Ming

2012-11-29

The importance of aerosols to humankind is well-known, playing an integral role in determining Earth's climate and influencing human health. Despite this fact, much remains unknown about the initial events of nucleation. In this work, the molecular properties of common organic atmospheric pollutant oxalic acid and its gas phase interactions with water have been thoroughly examined. Local minima single-point energies for the monomer conformations were calculated at the B3LYP and MP2 level of theory with both 6-311++G(d,p) and aug-cc-pVDZ basis sets and are compared with previous works. Optimized geometries, relative energies, and free energy changes for the stable clusters of oxalic acid conformers with up to six waters were then obtained from B3LYP calculations with 6-31+G(d) and 6-311++G(d,p) basis sets. Initially, cooperative binding is predicted to be the most important factor in nucleation, but as the clusters grow, dipole cancellations are found to play a pivotal role. The clusters of oxalic acid hydrated purely with water tend to produce extremely stable and neutral core systems. Free energies of formation and atmospheric implications are discussed.

Acute oxalate nephropathy after ingestion of star fruit.

PubMed

Chen, C L; Fang, H C; Chou, K J; Wang, J S; Chung, H M

2001-02-01

Acute oxalate nephropathy associated with ingestion of star fruit (carambola) has not been reported before. We report the first two cases. These patients developed nausea, vomiting, abdominal pain, and backache within hours of ingesting large quantities of sour carambola juice; then acute renal failure followed. Both patients needed hemodialysis for oliguric acute renal failure, and pathologic examinations showed typical changes of acute oxalate nephropathy. The renal function recovered 4 weeks later without specific treatment. Sour carambola juice is a popular beverage in Taiwan. The popularity of star fruit juice is not compatible with the rare discovery of star fruit-associated acute oxalate nephropathy. Commercial carambola juice usually is prepared by pickling and dilution processes that reduce oxalate content markedly, whereas pure fresh juice or mild diluted postpickled juice for traditional remedies, as used in our cases, contain high quantities of oxalate. An empty stomach and dehydrated state may pose an additional risk for development of renal injury. To avoid acute oxalate nephropathy, pure sour carambola juice or mild diluted postpickled juice should not be consumed in large amounts, especially on an empty stomach or in a dehydrated state.

Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

PubMed

Yin, Jun; Hu, Ying; Yoon, Juyoung

2015-07-21

All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems.

Response to Dietary Oxalate after Bariatric Surgery

PubMed Central

Froeder, Leila; Arasaki, Carlos Haruo; Malheiros, Carlos Alberto; Baxmann, Alessandra Calábria

2012-01-01

Summary Background and objectives Bariatric surgery (BS) may be associated with increased oxalate excretion and a higher risk of nephrolithiasis. This study aimed to investigate urinary abnormalities and responses to an acute oxalate load as an indirect assessment of the intestinal absorption of oxalate in this population. Design, setting, participants, & measurements Twenty-four–hour urine specimens were collected from 61 patients a median of 48 months after BS (post-BS) as well as from 30 morbidly obese (MO) participants; dietary information was obtained through 24-hour food recalls. An oral oxalate load test (OLT), consisting of 2-hour urine samples after overnight fasting and 2, 4, and 6 hours after consuming 375 mg of oxalate (spinach juice), was performed on 21 MO and 22 post-BS patients 12 months after BS. Ten post-BS patients also underwent OLT before surgery (pre-BS). Results There was a higher percentage of low urinary volume (<1.5 L/d) in post-BS versus MO (P<0.001). Hypocitraturia and hyperoxaluria (P=0.13 and P=0.36, respectively) were more frequent in BS versus MO patients. The OLT showed intragroup (P<0.001 for all periods versus baseline) and intergroup differences (P<0.001 for post-BS versus MO; P=0.03for post-BS versus pre-BS). The total mean increment in oxaluria after 6 hours of load, expressed as area under the curve, was higher in both post-BS versus MO and in post-BS versus pre-BS participants (P<0.001 for both). Conclusions The mean oxaluric response to an oxalate load is markedly elevated in post-bariatric surgery patients, suggesting that increased intestinal absorption of dietary oxalate is a predisposing mechanism for enteric hyperoxaluria. PMID:23024163

Growth Conditions To Reduce Oxalic Acid Content of Spinach

NASA Technical Reports Server (NTRS)

Johnson-Rutzke, Corinne

2003-01-01

A controlled-environment agricultural (CEA) technique to increase the nutritive value of spinach has been developed. This technique makes it possible to reduce the concentration of oxalic acid in spinach leaves. It is desirable to reduce the oxalic acid content because oxalic acid acts as an anti-nutritive calcium-binding component. More than 30 years ago, an enzyme (an oxidase) that breaks down oxalic acid into CO2 and H2O2 was discovered and found to be naturally present in spinach leaves. However, nitrate, which can also be present because of the use of common nitratebased fertilizers, inactivates the enzyme. In the CEA technique, one cuts off the supply of nitrate and keeps the spinach plants cool while providing sufficient oxygen. This technique provides the precise environment that enables the enzyme to naturally break down oxalate. The result of application of this technique is that the oxalate content is reduced by 2/3 in one week.

Oxalate content of some common foods: determination by an enzymatic method.

PubMed

Kasidas, G P; Rose, G A

1980-08-01

A specific enzymatic method was used to determine the oxalate content of some common foods. No preliminary isolation of oxalate was required and recoveries ranging from 95-110 per cent were obtained. Spinach, rhubarb, peanuts, chocolates, parsley and tea were found to contain high levels of oxalate as previously described by others. On the other hand the oxalate content of beetroot was found to be five times as high as previously reported, but coca-cola and beer were almost free from oxalate. Cereals and meat were either low or deficient in oxalate.

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

PubMed Central

Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

2016-01-01

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

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

Manna, Kuntal; Ji, Pengfei; Lin, Zekai

2016-08-30

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less

Oxalate nephropathy associated with chronic pancreatitis.

PubMed

Cartery, Claire; Faguer, Stanislas; Karras, Alexandre; Cointault, Olivier; Buscail, Louis; Modesto, Anne; Ribes, David; Rostaing, Lionel; Chauveau, Dominique; Giraud, Patrick

2011-08-01

Enteric overabsorption of oxalate may lead to hyperoxaluria and subsequent acute oxalate nephritis (AON). AON related to chronic pancreatitis is a rare and poorly described condition precluding early recognition and treatment. We collected the clinical characteristics, treatment, and renal outcome of 12 patients with chronic pancreatitis-associated AON followed in four French renal units. Before AON, mild to moderate chronic kidney disease was present in all patients, diabetes mellitus in eight (insulin [n = 6]; oral antidiabetic drugs [n = 2]), and known chronic pancreatitis in only eight. At presentation, pancreas imaging showed gland atrophy/heterogeneity, Wirsung duct dilation, calcification, or pseudocyst. Renal findings consisted of rapidly progressive renal failure with tubulointerstitial profile. Acute modification of glomerular filtration preceded the AON (i.e., diarrhea and diuretics). Increase in urinary oxalate excretion was found in all tested patients and hypocalcemia in nine (<1.5 mmol/L in four patients). Renal biopsy showed diffuse crystal deposits, highly suggestive of oxalate crystals, with tubular necrosis and interstitial inflammatory cell infiltrates. Treatment consisted of pancreatic enzyme supplementation, oral calcium intake, and an oxalate-free diet in all patients and renal replacement therapy in five patients. After a median follow-up of 7 months, three of 12 patients reached end-stage renal disease. AON is an under-recognized severe crystal-induced renal disease with features of tubulointerstitial nephritis that may occur in patients with a long history of chronic pancreatitis or reveal the pancreatic disease. Extrinsic triggering factors should be prevented.

DETERMINATION OF OXALATE ION DOPANT LEVEL IN POLYPYRROLE USING FT-IR

PubMed Central

Benally, Kristal J.; GreyEyes, Shawn D.; McKenzie, Jason T.

2014-01-01

A pellet method using standard addition and FT-IR was used to estimate oxalate ion doping levels in electrosynthesized polypyrrole. The method is useful for materials where removal of analyte from an insoluble material is problematic. Here, electrosynthesized oxalate doped polypyrrole is dispersed in potassium bromide. Spikes of sodium oxalate are added and the mixtures pressed into pellets. The oxalate carbonyl absorption peak is then used to quantify the amount of oxalate present in the polypyrrole. The mass fraction of oxalate dopant in polypyrrole was determined to be 0.4 ± 0.1 % and coincides with the original synthesis solution composition. PMID:25598749

The promotion effect of coexisting hygroscopic composition on the reaction between oxalic acid and calcite during humidifying process

NASA Astrophysics Data System (ADS)

Ma, Q.; He, H.

2012-12-01

Internally mixed oxalic acid with mineral dust has been frequently detected in field measurements (Sullivan and Prather, 2007; Wang et al., 2012; Yang et al., 2009). Meanwhile, Furukawa and Takahashi (Furukawa and Takahashi, 2011) found that most of the oxalic acid in mineral mixture is present as metal oxalate complexes in the aerosols, however, the formation mechanism of these complexes is not well known. It was reported that cloud process of H2C2O4/CaCO3 mixture could lead to the formation of calcium oxalate (Gierlus et al., 2012). Recently, we used Raman spectroscopy to investigate the hygroscopic behavior of H2C2O4/CaCO3 mixture below saturation condition as well as the effect of coexisting hygroscopic compositions, e.g. Ca(NO3)2, NaCl, NH4NO3, and (NH4)2SO4. It was found that there was no interaction between H2C2O4 and calcite without third component during humidifying process under ambient condition. In contrast, the presence of coexisting Ca(NO)3, NaCl, or NH4NO3 could promote the reaction between H2C2O4 and calcite by providing an aqueous circumstance after deliquescence, resulting in the formation of calcium oxalate hydrates. Moreover, substitution of strong acid (HNO3) by medium acid (H2C2O4) occurred when water vapor was absorbed in Ca(NO3)2/H2C2O4 mixture (Ma and He, 2012). As for (NH4)2SO4, there existed a competition effect between (NH4)2SO4 and H2C2O4 for the reaction with CaCO3. CaCO3 was preferentially reacted with (NH4)2SO4 to form gypsum in the solution, while the residual NH4+ and C2O42- ions were bonded to (NH4)2C2O4 after efflorescence. These results implies a potential formation pathway of metal oxalate complexes in the atmosphere and also suggests that synergistic effect between different constituents in humidifying process of mixed particles should be considered in future hygroscopic behavior studies.

Neurotoxic effects of carambola in rats: the role of oxalate.

PubMed

Chen, Chien-Liang; Chou, Kang-Ju; Wang, Jyh-Seng; Yeh, Jeng-Hsien; Fang, Hua-Chang; Chung, Hsiao-Min

2002-05-01

Carambola (star fruit) has been reported to contain neurotoxins that cause convulsions, hiccups, or death in uremic patients, and prolong barbiturate-induced sleeping time in rats. The constituent responsible for these effects remains uncertain. Carambola contains a large quantity of oxalate, which can induce depression of cerebral function and seizures. This study was conducted to investigate the role of oxalate in carambola toxicity in rats. The effects on barbiturate-induced sleeping time and death caused by intraperitoneal administration of carambola juice were observed in Sprague-Dawley rats. To obtain a dose-dependent response curve and evaluate the lethal dose, rats were treated with serial amounts of pure carambola juice diluted with normal saline in a volume of 1:1. To test the role of oxalate in the neurotoxic effect of carambola, either 5.33 g/kg carambola after oxalate removal or 5.33 g/kg of pure carambola juice diluted with normal saline were administered intraperitoneally, while the control group was given normal saline before pentobarbital injection. The effects of carambola and oxalate-removed carambola on barbiturate-induced sleeping time were compared with those of saline. To assess the lethal effect of oxalate in carambola, we gave rats chemical oxalate at comparable concentrations to the oxalate content of carambola. Carambola juice administration prolonged barbiturate-induced sleeping time in a dose-dependent manner. The sleeping time of rats that received normal saline and 1.33 g/kg, 2.67 g/kg, 5.33 g/kg, and 10.67 g/kg of carambola juice were 66 +/- 16.6, 93.7 +/- 13.4, 113.3 +/- 11.4, 117.5 +/- 29.0, and 172.5 +/- 38.8 minutes, respectively. The three higher-dose groups had longer sleeping times than controls (p < 0.05 or 0.005). This effect was eliminated after the removal of oxalate from carambola juice. Four of eight rats in the 10.67-g/kg group and all rats in the 21.33 g/kg and chemical oxalate groups died after seizure. Lethal doses

Engineering calcium oxalate crystal formation in Arabidopsis

USDA-ARS?s Scientific Manuscript database

Many plants accumulate crystals of calcium oxalate. Just how these crystals form remains unknown. To gain insight into the mechanisms regulating calcium oxalate crystal formation, a crystal engineering approach was initiated utilizing the non-crystal accumulating plant, Arabidopsis. The success of t...

Association analysis for oxalate concentration in spinach

USDA-ARS?s Scientific Manuscript database

Screening and breeding low-oxalate germplasm is a major objective in spinach breeding. This research aims to conduct association analysis and identify SNP markers associated with oxalate concentration in spinach germplasm. A total of 310 spinach genotypes including 300 USDA germplasm accessions and ...

A semi-micromethod for determination of oxalate in human plasma.

PubMed

Porowski, Tadeusz; Gałasiński, Władysław

2003-01-01

An enzymatic semi-micromethod for oxalate determination in human plasma was elaborated. The principle of the method depends on the oxalate isolation from deproteinized plasma, following determination by the calorimetric oxalate oxidase-peroxidase-indamine system. This method protects against internal oxalate losses and excludes an interference of contaminations. Results, obtained by this method, were reliable and ideally suited for use as real normal values (less than or equal to 6 microM) of oxalate content in the plasma of healthy individuals. The elaborated method, which can assay plasma oxalate accurately in normal individuals as well as in hyperoxalemic conditions is superior to those previously used. The procedure of semi-micromethod does not require expensive equipments and apparatus: it is simple and easy to perform in every laboratory and takes little time.

Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

PubMed

Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

2013-06-15

The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. Copyright © 2013 Elsevier B.V. All rights reserved.

Contribution of calcium oxalate to soil-exchangeable calcium

USGS Publications Warehouse

Dauer, Jenny M.; Perakis, Steven S.

2013-01-01

Acid deposition and repeated biomass harvest have decreased soil calcium (Ca) availability in many temperate forests worldwide, yet existing methods for assessing available soil Ca do not fully characterize soil Ca forms. To account for discrepancies in ecosystem Ca budgets, it has been hypothesized that the highly insoluble biomineral Ca oxalate might represent an additional soil Ca pool that is not detected in standard measures of soil-exchangeable Ca. We asked whether several standard method extractants for soil-exchangeable Ca could also access Ca held in Ca oxalate crystals using spike recovery tests in both pure solutions and soil extractions. In solutions of the extractants ammonium chloride, ammonium acetate, and barium chloride, we observed 2% to 104% dissolution of Ca oxalate crystals, with dissolution increasing with both solution molarity and ionic potential of cation extractant. In spike recovery tests using a low-Ca soil, we estimate that 1 M ammonium acetate extraction dissolved sufficient Ca oxalate to contribute an additional 52% to standard measurements of soil-exchangeable Ca. However, in a high-Ca soil, the amount of Ca oxalate spike that would dissolve in 1 M ammonium acetate extraction was difficult to detect against the large pool of exchangeable Ca. We conclude that Ca oxalate can contribute substantially to standard estimates of soil-exchangeable Ca in acid forest soils with low soil-exchangeable Ca. Consequently, measures of exchangeable Ca are unlikely to fully resolve discrepancies in ecosystem Ca mass balance unless the contribution of Ca oxalate to exchangeable Ca is also assessed.

Medical therapy, calcium oxalate urolithiasis

NASA Technical Reports Server (NTRS)

Ruml, L. A.; Pearle, M. S.; Pak, C. Y.

1997-01-01

The development of diagnostic protocols that identify specific risk factors for calcium oxalate nephrolithiasis has led to the formulation of directed medical regimens that are aimed at correcting the underlying metabolic disturbances. Initiation of these treatment programs has reduced markedly the rate of stone formation in the majority of patients who form stones. This article discusses the rationale that underlies the choice of medical therapy for the various pathophysiologic causes of calcium oxalate nephrolithiasis and the appropriate use of available medications.

Calcium oxalate contribution to calcium cycling in forests of contrasting nutrient status

USGS Publications Warehouse

Dauer, Jenny M.; Perakis, Steven S.

2014-01-01

Calcium oxalate (Ca oxalate) is an insoluble biomineral that forms in plants and fungi, and occurs in soils across many types of ecosystems. Assessing how Ca oxalate may shape ecosystem Ca cycling requires information on the distribution of Ca oxalate among plant biomass, detritus, and mineral soil, and how it varies with ecosystem Ca status. We compared two Douglas-fir forests of contrasting ecosystem Ca availability, and found that Ca oxalate was partitioned similarly among plant biomass, detritus and mineral soil major ecosystem compartments at both sites, and total pools of Ca oxalate were greater in the high-Ca forest. However, the proportional importance of Ca oxalate was greater in the low-Ca than high-Ca forest (18% versus 4% of actively cycling ecosystem Ca, respectively). And calcium oxalate in mineral soil, which is of particular interest as a potential long-term Ca reservoir, was a larger portion of total available Ca (exchangeable Ca plus Ca oxalate Ca) in the low-Ca site than the high-Ca site (9% versus 1% of available soil Ca, respectively). Calcium oxalate was the dominant form of Ca returned from plants to soil as leaf litterfall at the high-Ca site, yet calcium oxalate disappeared rapidly from decomposing litter (0.28 yr−1 or faster) at both sites. We conclude that accumulation of Ca oxalate in forest ecosystems appears most closely related to overall Ca supply for live biomass pools, and that the accumulation of Ca oxalate in forest floor and mineral soil is limited by rapid microbial degradation of putatively unavailable Ca oxalate.

First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Kaneko, Tomoaki; Saito, Riichiro

2017-11-01

Energetics and electronic structures of alkali metal (Li, Na, K, Rb, and Cs) and alkaline earth metal (Be, Mg, Ca, Sr, and Ba) atoms intercalated bilayer graphene are systematically investigated using first-principles calculations based on density functional theory. Formation of alkali and alkaline earth metal atoms intercalated bilayer graphene is exothermic except for Be and Mg. The interlayer state between two graphene layers is occupied for K, Rb, Cs, Ca, Sr, and Ba. We find that the energetic position of the interlayer states between bilayer graphene monotonically shifts downward with increasing of interlayer distance. The interlayer distances of more than 4.5 Å and 4.0 Å, respectively, are necessary for the occupation of the interlayer state in bilayer graphene for alkali and alkaline earth metal atoms, which is almost independent of the intercalant metal species. We discuss the relevance to occurrence of superconductivity for the metal intercalated bilayer graphene in terms of the occupation of the interlayer state and the phonon frequency of metal ions.

Molten metal containment vessel with rare earth oxysulfide protective coating thereon and method of making same

DOEpatents

Krikorian, Oscar H.; Curtis, Paul G.

1992-01-01

An improved molten metal containment vessel is disclosed in which wetting of the vessel's inner wall surfaces by molten metal is inhibited by coating at least the inner surfaces of the containment vessel with one or more rare earth oxysulfide or rare earth sulfide compounds to inhibit wetting and or adherence by the molten metal to the surfaces of the containment vessel.

New Approach to Remove Metals from Chromated Copper Arsenate (CCA)-Treated Wood

Treesearch

Todd F. Shupe; Chung Y. Hse; Hui Pan

2012-01-01

Recovery of metals from chromated copper arsenate (CCA)-treated southern pine wood particles was investigated using binary acid solutions consisting of acetic, oxalic, and phosphoric acids in a microwave reactor. Formation of an insoluble copper oxalate complex in the binary solution containing oxalic acid was the major factor for low copper removal. Furthermore, the...

Enhanced stabilization of Pb, Zn, and Cd in contaminated soils using oxalic acid-activated phosphate rocks.

PubMed

Zhang, Zhuo; Guo, Guanlin; Wang, Mei; Zhang, Jia; Wang, Zhixin; Li, Fasheng; Chen, Honghan

2018-01-01

Phosphate amendments, especially phosphate rock (PR), are one of the most commonly used materials to stabilize heavy metals in contaminated soils. However, most of PR reserve consists of low-grade ore, which limits the efficiency of PR for stabilizing heavy metals. This study was to enhance the stabilization of heavy metals through improving the available phosphorous (P) release of PR by oxalic acid activation. Raw PR and activated PR (APR) were characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET) surface analysis, and laser diffraction to determine the changes of structure and composition of APR. The stabilization effectiveness of lead (Pb), zinc (Zn), and cadmium (Cd) in soils by APR was investigated through toxicity leaching test and speciation analysis. The results indicated that after treatment by oxalic acid, (1) the crystallinity of the fluorapatite phase of PR transformed into the weddellite phase; (2) the surface area of PR increased by 37%; (3) the particle size of PR became homogenized (20-70 μm); and (4) the available P content in PR increased by 22 times. These changes of physicochemical characteristics of PR induced that APR was more effective to transform soil heavy metals from the non-residual fraction to the residual fraction and enhance the stabilization efficiency of Pb, Zn, and Cd than PR. These results are significant for the future use of low-grade PR to stabilize heavy metals.

Method and apparatus for the production of metal oxide powder

DOEpatents

Harris, Michael T.; Scott, Timothy C.; Byers, Charles H.

1993-01-01

The present invention provides a method for preparing metal oxide powder. A first solution, which is substantially organic, is prepared. A second solution, which is an aqueous solution substantially immiscible in the first solution, is prepared and delivered as drops to the first solution. The drops of the second solution are atomized by a pulsed electric field forming micro-drops of the second solution. Reagents in the first solution diffuse into and react with reactants in the micro-drops of the second solution forming metal hydroxide or oxalate particles. The metal hydroxide or metal oxalate particles are then recovered and dried to produce the metal oxide powder. An apparatus for preparing a metal oxide powder is also disclosed.

Method and apparatus for the production of metal oxide powder

DOEpatents

Harris, Michael T.; Scott, Timothy C.; Byers, Charles H.

1992-01-01

The present invention provides a method for preparing metal oxide powder. A first solution, which is substantially organic, is prepared. A second solution, which is an aqueous solution substantially immiscible in the first solution, is prepared and delivered as drops to the first solution. The drops of the second solution are atomized by a pulsed electric field forming micro-drops of the second solution. Reagents in the first solution diffuse into and react with reactants in the micro-drops of the second solution forming metal hydroxide or oxalate particles. The metal hydroxide or metal oxalate particles are then recovered and dried to produce the metal oxide powder. An apparatus for preparing a metal oxide powder is also disclosed.

Effect of heat treatment on the structure of incorporated oxalate species and photoluminescent properties of porous alumina films formed in oxalic acid

NASA Astrophysics Data System (ADS)

Vrublevsky, I.; Jagminas, A.; Hemeltjen, S.; Goedel, W. A.

2008-09-01

The present work focuses on the use of IR spectroscopy and photoluminescence spectral measurements for studying the treatment temperature effect on the compositional and luminescent properties of oxalic acid alumina films. In line with the recent researches we have also found that heat treatment of porous alumina films formed in oxalic acid leads to considerable changes in their photoluminescence properties: upon annealing the intensity of photoluminescence (PL) increases reaching a maximum at the temperature of around 500 °C and then decreases. IR spectra of as-grown and heat-treated films have proved that PL emission in the anodic alumina films is related with the state of 'structural' oxalate species incorporated in the oxide lattice. These results allowed us to conclude that PL behavior of oxalic acid alumina films can be explained through the concept of variations in the bonding molecular orbitals of incorporated oxalate species including σ- and π-bonds.

Low frequency vibrational spectra and the nature of metal-oxygen bond of alkaline earth metal acetylacetonates

NASA Astrophysics Data System (ADS)

Fakheri, Hamideh; Tayyari, Sayyed Faramarz; Heravi, Mohammad Momen; Morsali, Ali

2017-12-01

Theoretical quantum chemistry calculations were used to assign the observed vibrational band frequencies of Be, Mg, Ca, Sr, and Ba acetylacetonates complexes. Density functional theory (DFT) calculations have been carried out at the B3LYP level, using LanL2DZ, def2SVP, and mixed, GenECP, (def2SVP for metal ions and 6-311++G** for all other atoms) basis sets. The B3LYP level, with mixed basis sets, was utilized for calculations of vibrational frequencies, IR intensity, and Raman activity. Analysis of the vibrational spectra indicates that there are several bands which could almost be assigned mainly to the metal-oxygen vibrations. The strongest Raman band in this region could be used as a measure of the stability of the complex. The effects of central metal on the bond orders and charge distributions in alkaline earth metal acetylacetonates were studied by the Natural Bond Orbital (NBO) method for fully optimized compounds. Optimization were performed at the B3LYP/6-311++G** level for the lighter alkaline earth metal complexes (Be, Mg, and Ca acetylacetonates) while the B3LYP level, using LanL2DZ (extrabasis, d and f on oxygen and metal atoms), def2SVP and mixed (def2SVP on metal ions and 6-311++G** for all other atoms) basis sets for all understudy complexes. Calculations indicate that the covalence nature of metal-oxygen bonds considerably decreases from Be to Ba complexes. The nature of metal-oxygen bond was further studied by using Atoms In Molecules (AIM) analysis. The topological parameters, Wiberg bond orders, natural charges of O and metal ions, and also some vibrational band frequencies were correlated with the stability constants of understudy complexes.

High Pressure Phase Transformations in Heavy Rare Earth Metals and Connections to Actinide Crystal Structures

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

Vohra, Yogesh K.; Sangala, Bagvanth Reddy; Stemshorn, Andrew K.

2008-07-01

High-pressure studies have been performed on heavy rare earth metals Terbium (Tb) to 155 GPa and Holmium (Ho) to 134 GPa in a diamond anvil cell at room temperature. The following crystal structure sequence was observed in both metals hcp {yields} Sm-type {yields} dhcp {yields} distorted fcc (hR-24) {yields} monoclinic (C2/m) with increasing pressure. The last transformation to a low symmetry monoclinic phase is accompanied by a volume collapse of 5 % for Tb at 51 GPa and a volume collapse of 3 % for Ho at 103 GPa. This volume collapse under high pressure is reminiscent of f-shell delocalizationmore » in light rare earth metal Cerium (Ce), Praseodymium (Pr), and heavy actinide metals Americium (Am) and Curium (Cm). The orthorhombic Pnma phase that has been reported in Am and Cm after f-shell delocalization is not observed in heavy rare earth metals under high pressures. (authors)« less

A Human Strain of Oxalobacter (HC-1) Promotes Enteric Oxalate Secretion in the Small Intestine of Mice and Reduces Urinary Oxalate Excretion

PubMed Central

Hatch, Marguerite; Freel, Robert W.

2013-01-01

Enteric oxalate secretion that correlated with reductions in urinary oxalate excretion was previously reported in a mouse model of Primary Hyperoxaluria, and in wild type (WT) mice colonized with a wild rat strain (OXWR) of Oxalobacter (Am J Physiol 300: G461-G469, 2011). Since a human strain of the bacterium is more likely to be clinically used as a probiotic therapeutic, we tested the effects of HC-1 in WT. Following artificial colonization of WT mice with HC-1, the bacteria were confirmed to be present in the large intestine and, unexpectedly, detected in the small intestine for varying periods of time. The main objective of the present study was to determine whether the presence of HC-1 promoted intestinal secretion in the more proximal segments of the gastrointestinal tract. In addition, we determined whether HC-1 colonization led to reductions in urinary oxalate excretion in these mice. The results show that the human Oxalobacter strain promotes a robust net secretion of oxalate in the distal ileum as well as in the caecum and distal colon and these changes in transport correlate with the beneficial effect of reducing renal excretion of oxalate. We conclude that OXWR effects on intestinal oxalate transport and oxalate homeostasis are not unique to the wild rat strain and that, mechanistically, HC-1 has significant potential for use as a probiotic treatment for hyperoxaluria especially if it is also targeted to the upper and lower gastrointestinal tract. PMID:23959075

Microbial Community Transplant Results in Increased and Long-Term Oxalate Degradation

PubMed Central

Miller, Aaron W.; Oakeson, Kelly F.; Dale, Colin; Dearing, M. Denise

2016-01-01

Gut microbes are essential for the degradation of dietary oxalate, and this function may play a role in decreasing the incidence of kidney stones. However, many oxalate-degrading bacteria are susceptible to antibiotics and the use of oxalate-degrading probiotics has only led to an ephemeral reduction in urinary oxalate. The objective of the current study was to determine the efficacy of using whole-community microbial transplants from a wild mammalian herbivore, Neotoma albigula, to increase oxalate degradation over the long term in the laboratory rat, Rattus norvegicus. We quantified the change in total oxalate degradation in lab rats immediately after microbial transplants and at 2- and 9-month intervals following microbial transplants. Additionally, we tracked the fecal microbiota of the lab rats, with and without microbial transplants, using high-throughput Illumina sequencing of a hyper-variable region of the 16S rRNA gene. Microbial transplants resulted in a significant increase in oxalate degradation, an effect that persisted 9 months after the initial transplants. Functional persistence was corroborated by the transfer, and persistence of a group of bacteria previously correlated with oxalate consumption in N. albigula, including an anaerobic bacterium from the genus Oxalobacter known for its ability to use oxalate as a sole carbon source. The results of this study indicate that whole-community microbial transplants are an effective means for the persistent colonization of oxalate-degrading bacteria in the mammalian gut. PMID:27312892

Flow-driven pattern formation in the calcium-oxalate system.

PubMed

Bohner, Bíborka; Endrődi, Balázs; Horváth, Dezső; Tóth, Ágota

2016-04-28

The precipitation reaction of calcium oxalate is studied experimentally in the presence of spatial gradients by controlled flow of calcium into oxalate solution. The density difference between the reactants leads to strong convection in the form of a gravity current that drives the spatiotemporal pattern formation. The phase diagram of the system is constructed, the evolving precipitate patterns are analyzed and quantitatively characterized by their diameters and the average height of the gravity flow. The compact structures of calcium oxalate monohydrate produced at low flow rates are replaced by the thermodynamically unstable calcium oxalate dihydrate favored in the presence of a strong gravity current.

Dissolution of Simulated and Radioactive Savannah River Site High-Level Waste Sludges with Oxalic Acid & Citric Acid Solutions

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

STALLINGS, MARY

untreated sludge solids. We recommend that these results be evaluated further to determine if these solutions contain sufficient neutron poisons. We observed low general corrosion rates in tests in which carbon steel coupons were contacted with solutions of oxalic acid, citric acid and mixtures of oxalic and citric acids. Wall thinning can be minimized by maintaining short contact times with these acid solutions. We recommend additional testing with oxalic and oxalic/citric acid mixtures to measure dissolution performance of sludges that have not been previously dried. This testing should include tests to clearly ascertain the effects of total acid strength and metal complexation on dissolution performance. Further work should also evaluate the downstream impacts of citric acid on the SRS High-Level Waste System (e.g., radiochemical separations in the Salt Waste Processing Facility and addition of organic carbon in the Saltstone and Defense Waste Processing facilities).« less

Effects of Juice Processing on Oxalate Contents in Carambola Juice Products.

PubMed

Huynh, Nha K; Nguyen, Ha V H

2017-09-01

Effects of processing methods including pressing, enzyme-assisted extraction, lactic acid fermentation by Lactobacillus acidophilus, and alcohol fermentation by Saccharomyces cerevisiae on total and soluble oxalate contents of carambola juices were studied. In comparison with pressing, the use of enzyme increased juice yields (15.89-17.29%), but resulted in higher total oxalate (1.60-1.73 times) and soluble oxalate contents (1.16-1.49 times). In addition, extension of enzyme incubation periods led to an increase in soluble oxalate contents in the products (p < 0.05). On the other hand, alcohol fermentation with Saccharomyces cerevisiae from 1 to 5 weeks reduced 37-58% of total oxalate and 39-59% of soluble oxalate contents. Prolonged fermentation also demonstrated better reduction of oxalate contents. Meanwhile, lactic acid fermentation using Lactobacillus acidophilus had no effects on total and soluble oxalate contents in carambola juices. These results suggested that carambola juice products should only be consumed moderately, and that alcohol fermentation could be a potential method to reduce oxalate contents in foods in order to prevent the risks of forming kidney stones.

Method and apparatus for the production of metal oxide powder

DOEpatents

Harris, M.T.; Scott, T.C.; Byers, C.H.

1992-06-16

The present invention provides a method for preparing metal oxide powder. A first solution, which is substantially organic, is prepared. A second solution, which is an aqueous solution substantially immiscible in the first solution, is prepared and delivered as drops to the first solution. The drops of the second solution are atomized by a pulsed electric field forming micro-drops of the second solution. Reagents in the first solution diffuse into and react with reactants in the micro-drops of the second solution forming metal hydroxide or oxalate particles. The metal hydroxide or metal oxalate particles are then recovered and dried to produce the metal oxide powder. An apparatus for preparing a metal oxide powder is also disclosed. 2 figs.

Evidence for net renal tubule oxalate secretion in patients with calcium kidney stones

PubMed Central

Zisman, Anna L.; Asplin, John R.; Worcester, Elaine M.; Coe, Fredric L.

2011-01-01

Little is known about the renal handling of oxalate in patients with idiopathic hypercalciuria (IH). To explore the role of tubular oxalate handling in IH and to evaluate whether differences exist between IH and normal controls, we studied 19 IH subjects, 8 normal subjects, and 2 bariatric stone formers (BSF) during a 1-day General Clinical Research Center protocol utilizing a low-oxalate diet. Urine and blood samples were collected at 30- to 60-min intervals while subjects were fasting and after they ate three meals providing known amounts of calcium, phosphorus, sodium, protein, oxalate, and calories. Plasma oxalate concentrations and oxalate-filtered loads were similar between patients (includes IH and BSF) and controls in both the fasting and fed states. Urinary oxalate excretion was significantly higher in patients vs. controls regardless of feeding state. Fractional excretion of oxalate (FEOx) was >1, suggesting tubular secretion of oxalate, in 6 of 19 IH and both BSF, compared with none of the controls (P < 0.00001). Adjusted for water extraction along the nephron, urine oxalate rose more rapidly among patients than normal subjects with increases in plasma oxalate. Our findings identify tubular secretion of oxalate as a key mediator of hyperoxaluria in calcium stone formers, potentially as a means of maintaining plasma oxalate in a tight range. PMID:21123489

Microbial growth on oxalate by a route not involving glyoxylate carboligase

PubMed Central

Blackmore, Maureen A.; Quayle, J. R.

1970-01-01

1. The metabolism of oxalate by the pink-pigmented organisms, Pseudomonas AM1, Pseudomonas AM2, Protaminobacter ruber and Pseudomonas extorquens has been compared with that of the non-pigmented Pseudomonas oxalaticus. 2. During growth on oxalate, all the organisms contain oxalyl-CoA decarboxylase, formate dehydrogenase and oxalyl-CoA reductase. This is consistent with oxidation of oxalate to carbon dioxide taking place via oxalyl-CoA, formyl-CoA and formate as intermediates, and also reduction of oxalate to glyoxylate taking place via oxalyl-CoA. 3. The pink-pigmented organisms, when grown on oxalate, contain l-serine–glyoxylate aminotransferase and hydroxypyruvate reductase but do not contain glyoxylate carboligase. The converse of this obtains in oxalate-grown Ps. oxalaticus. This indicates that, in contrast with Ps. oxalaticus, synthesis of C3 compounds from oxalate by the pink-pigmented organisms occurs by a variant of the `serine pathway' used by Pseudomonas AM1 during growth on C1 compounds. 4. Evidence in favour of this scheme is provided by the finding that a mutant of Pseudomonas AM1 that lacks hydroxypyruvate reductase is not able to grow on oxalate. PMID:5472155

Alterations of thorium oxalate morphology by changing elementary precipitation conditions

NASA Astrophysics Data System (ADS)

Tyrpekl, V.; Beliš, M.; Wangle, T.; Vleugels, J.; Verwerft, M.

2017-09-01

Oxalates of actinide elements are widely used in research and industry mainly due to their low solubility in aqueous solution and easy conversion to oxide. Although thorium oxide is worldwide mostly produced by the oxalate precipitation and conversion route, the powder morphology obtained through this process is known to inhibit the packing and sintering step of the pellet production. The presented work investigates the effects of oxalate precipitation conditions on the final powder morphology. Among the precipitation conditions considered are: pH of the thorium feed solution, concentration, temperature and the order of addition (thorium solution in oxalic acid solution and vice versa) known as reverse/direct strike. Herein, we show that the morphology of the final oxalate depends significantly on the above mentioned precipitation parameters.

Cholinergic signaling inhibits oxalate transport by human intestinal T84 cells

PubMed Central

Cheng, Ming; Aronson, Peter S.

2012-01-01

Urolithiasis remains a very common disease in Western countries. Seventy to eighty percent of kidney stones are composed of calcium oxalate, and minor changes in urinary oxalate affect stone risk. Intestinal oxalate secretion mediated by anion exchanger SLC26A6 plays a major constitutive role in limiting net absorption of ingested oxalate, thereby preventing hyperoxaluria and calcium oxalate urolithiasis. Using the relatively selective PKC-δ inhibitor rottlerin, we had previously found that PKC-δ activation inhibits Slc26a6 activity in mouse duodenal tissue. To identify a model system to study physiologic agonists upstream of PKC-δ, we characterized the human intestinal cell line T84. Knockdown studies demonstrated that endogenous SLC26A6 mediates most of the oxalate transport by T84 cells. Cholinergic stimulation with carbachol modulates intestinal ion transport through signaling pathways including PKC activation. We therefore examined whether carbachol affects oxalate transport in T84 cells. We found that carbachol significantly inhibited oxalate transport by T84 cells, an effect blocked by rottlerin. Carbachol also led to significant translocation of PKC-δ from the cytosol to the membrane of T84 cells. Using pharmacological inhibitors, we observed that carbachol inhibits oxalate transport through the M3 muscarinic receptor and phospholipase C. Utilizing the Src inhibitor PP2 and phosphorylation studies, we found that the observed regulation downstream of PKC-δ is partially mediated by c-Src. Biotinylation studies revealed that carbachol inhibits oxalate transport by reducing SLC26A6 surface expression. We conclude that carbachol negatively regulates oxalate transport by reducing SLC26A6 surface expression in T84 cells through signaling pathways including the M3 muscarinic receptor, phospholipase C, PKC-δ, and c-Src. PMID:21956166

[Formation of oxalate in oxaliplatin injection diluted with infusion solutions].

PubMed

Eto, Seiji; Yamamoto, Kie; Shimazu, Kounosuke; Sugiura, Toshimune; Baba, Kaori; Sato, Ayaka; Goromaru, Takeshi; Hagiwara, Yoshiaki; Hara, Keiko; Shinohara, Yoshitake; Takahashi, Kojiro

2014-01-01

Oxaliplatin use can cause acute peripheral neuropathy characterized by sensory paresthesias, which are markedly exacerbated by exposure to cold temperatures, and is a dose-limiting factor in the treatment of colorectal cancer.Oxalate is eliminated in a series of nonenzymatic conversions of oxaliplatin in infusion solutions or biological fluids.Elimination of oxalate from oxaliplatin has been suggested as one of the reasons for the development of acute neuropathy.In this study, we developed a high-performance liquid chromatography(HPLC)-based method to detect oxalate formation, and investigated the time dependent formation of oxalate in oxaliplatin diluted with infusion solutions.The results obtained showed that the amount of oxalate in the solution corresponded to 1.6% of oxaliplatin 8 h after oxaliplatin dilution with a 5% glucose solution. On the other hand, oxalate formation from oxaliplatin diluted with a saline solution was ten-fold higher than that from oxaliplatin diluted with the 5% glucose solution.Most patients who were intravenously injected with oxaliplatin experienced venous pain.As a preventive measure against venous pain, dexamethasone was added to the oxaliplatin injection.We measured the amount of oxalate formed in the dexamethasone-containing oxaliplatin injection diluted with a 5% glucose solution.The amount of oxalate formed when dexamethasone was added did not differ significantly from that formed when dexamethasone was not added.Thus, there are no clinical problems associated with the stability of oxaliplatin solutions.

Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

PubMed

Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

2013-11-01

Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

PubMed

Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2016-10-04

Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

Bio-inspired Design of Electrocatalysts for Oxalate Oxidation: a Combined Experimental and Computational Study of Mn–N–C Catalysts

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

Matanovic, Ivana; Babanova, Sofia; Perry, Albert

2015-05-28

We report a novel non-platinum group metal (non-PGM) catalyst derived from Mn and amino- antipyrine (MnAAPyr) that shows electrochemical activity towards the oxidation of oxalic acid comparable to Pt with an onset potential for oxalate oxidation measured to be 0.714 * 0.002 V vs. SHE at pH = 4. The material has been synthesized using a templating Sacrificial Support Method with manganese nitrate and 4-aminoantipyrine as precursors. This catalyst is a nano-structured material in which Mn is atomically dispersed on a nitrogendoped graphene matrix. XPS studies reveal high abundance of pyridinic, Mn–Nx, and pyrrolic nitrogen pointing towards the conclusion thatmore » pyridinic nitrogen atoms coordinated to manganese constitute the active centers. Thus, the main features of the MnAAPyr catalyst are it exhibits similarity to the active sites of naturally occurring enzymes that are capable of efficient and selective oxidation of oxalic acid. Density functional theory in plane wave formalism with Perdew, Burke and Ernzerhof functional was further used to study the stability and activity of different one-metal active centers that could exist in the catalyst. The results show that the stability of the Mn–Nx sites changes in the following order: MnN4 4 MnN3C 4 MnN2C2 4 MnN3. Based on the overpotentials of 0.64 V and 0.71 V vs. SHE, calculated using the free energy diagrams for the oxalate oxidation mechanism, we could conclude that the MnN3C and MnN2C2 sites are most probable Mn–Nx sites responsible for the reported catalytic activity of the new catalyst.« less

Oxalobacter formigenes–Derived Bioactive Factors Stimulate Oxalate Transport by Intestinal Epithelial Cells

PubMed Central

Arvans, Donna; Jung, Yong-Chul; Antonopoulos, Dionysios; Koval, Jason; Granja, Ignacio; Bashir, Mohamed; Karrar, Eltayeb; Roy-Chowdhury, Jayanta; Musch, Mark; Asplin, John; Chang, Eugene

2017-01-01

Hyperoxaluria is a major risk factor for kidney stones and has no specific therapy, although Oxalobacter formigenes colonization is associated with reduced stone risk. O. formigenes interacts with colonic epithelium and induces colonic oxalate secretion, thereby reducing urinary oxalate excretion, via an unknown secretagogue. The difficulties in sustaining O. formigenes colonization underscore the need to identify the derived factors inducing colonic oxalate secretion. We therefore evaluated the effects of O. formigenes culture conditioned medium (CM) on apical 14C-oxalate uptake by human intestinal Caco-2-BBE cells. Compared with control medium, O. formigenes CM significantly stimulated oxalate uptake (>2.4-fold), whereas CM from Lactobacillus acidophilus did not. Treating the O. formigenes CM with heat or pepsin completely abolished this bioactivity, and selective ultrafiltration of the CM revealed that the O. formigenes–derived factors have molecular masses of 10–30 kDa. Treatment with the protein kinase A inhibitor H89 or the anion exchange inhibitor 4,4'-diisothiocyano-2,2'-stilbenedisulfonic acid completely blocked the CM-induced oxalate transport. Knockdown of the oxalate transporter SLC26A6 also significantly restricted the induction of oxalate transport by CM. In a mouse model of primary hyperoxaluria type 1, rectal administration of O. formigenes CM significantly reduced (>32.5%) urinary oxalate excretion and stimulated (>42%) distal colonic oxalate secretion. We conclude that O. formigenes–derived bioactive factors stimulate oxalate transport in intestinal cells through mechanisms including PKA activation. The reduction in urinary oxalate excretion in hyperoxaluric mice treated with O. formigenes CM reflects the in vivo retention of biologic activity and the therapeutic potential of these factors. PMID:27738124

High pressure phase transitions in the rare earth metal erbium to 151 GPa.

PubMed

Samudrala, Gopi K; Thomas, Sarah A; Montgomery, Jeffrey M; Vohra, Yogesh K

2011-08-10

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence hcp → Sm type → dhcp → distorted fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

High pressure phase transitions in the rare earth metal erbium to 151 GPa

NASA Astrophysics Data System (ADS)

Samudrala, Gopi K.; Thomas, Sarah A.; Montgomery, Jeffrey M.; Vohra, Yogesh K.

2011-08-01

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence {hcp} \\to {Sm}~ {type} \\to {dhcp} \\to {distorted} fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

Removal of arsenic and cadmium with sequential soil washing techniques using Na2EDTA, oxalic and phosphoric acid: Optimization conditions, removal effectiveness and ecological risks.

PubMed

Wei, Meng; Chen, Jiajun; Wang, Xingwei

2016-08-01

Testing of sequential soil washing in triplicate using typical chelating agent (Na2EDTA), organic acid (oxalic acid) and inorganic weak acid (phosphoric acid) was conducted to remediate soil contaminated by heavy metals close to a mining area. The aim of the testing was to improve removal efficiency and reduce mobility of heavy metals. The sequential extraction procedure and further speciation analysis of heavy metals demonstrated that the primary components of arsenic and cadmium in the soil were residual As (O-As) and exchangeable fraction, which accounted for 60% and 70% of total arsenic and cadmium, respectively. It was determined that soil washing agents and their washing order were critical to removal efficiencies of metal fractions, metal bioavailability and potential mobility due to different levels of dissolution of residual fractions and inter-transformation of metal fractions. The optimal soil washing option for arsenic and cadmium was identified as phosphoric-oxalic acid-Na2EDTA sequence (POE) based on the high removal efficiency (41.9% for arsenic and 89.6% for cadmium) and the minimal harmful effects of the mobility and bioavailability of the remaining heavy metals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Concentration gradient of oxalate from cortex to papilla in rat kidney.

PubMed

Nakatani, Tatsuya; Ishii, Keiichi; Sugimoto, Toshikado; Kamikawa, Sadanori; Yamamoto, Keisuke; Yoneda, Yukio; Kanazawa, Toshinao; Kishimoto, Taketoshi

2003-02-01

The kidney eliminates the major fraction of plasma oxalate. It is well known that oxalate is freely filtered by glomeruli and secreted by the proximal tubules. However, the renal handling of oxalate in distal nephrons, which is considered as playing an important role in stone formation, remains obscure. At 15-180 min after intravenous injection of 14C-oxalate to rats, the intrarenal localization of radioactivity was quantitatively measured by the radioluminographic method using a bioimaging analyzer. Tissue radioactivity was compared with plasma, and urinary radioactivities were measured by a liquid scintillation counter. The control study was conducted with 14C-inulin. The radioactivity of 14C-oxalate in the papilla was 10 times greater than in the cortex and eight times greater than in the medulla 180 min after injection when almost no radioactivity was present in the urine. In contrast, the radioactivity of 14C-inulin was nine times less in the papilla than in the cortex at the same time. Oxalate remains in the renal papilla for an extended period. This accumulation of oxalate may be attributed to calcium oxalate crystal fixation along the deep nephron which is considered to be the first step of stone formation.

Production and degradation of oxalic acid by brown rot fungi

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

Espejo, E.; Agosin, E.

1991-07-01

Our results show that all of the brown rot fungi tested produce oxalic acid in liquid as well as in semisolid cultures. Gloeophyllum trabeum, which accumulates the lowest amount of oxalic acid during decay of pine holocellulose, showed the highest polysaccharide-depolymerizing activity. Semisolid cultures inoculated with this fungus rapidly converted {sup 14}C-labeled oxalic acid to CO{sub 2} during cellulose depolymerization. The other brown rot fungi also oxidized {sup 14}C-labeled oxalic acid, although less rapidly. In contrast, semisolid cultures inoculated with the white rot fungus Coriolus versicolor did not significantly catabolize the acid and did not depolymerize the holocellulose during decay.more » Semisolid cultures of G. trabeum amended with desferrioxamine, a specific iron-chelating agent, were unable to lower the degree of polymerization of cellulose or to oxidize {sup 14}C-labeled oxalic acid to the extent or at the rate that control cultures did. These results suggest that both iron and oxalic acid are involved in cellulose depolymerization by brown rot fungi.« less

Pore-Environment Engineering with Multiple Metal Sites in Rare-Earth Porphyrinic Metal-Organic Frameworks.

PubMed

Zhang, Liangliang; Yuan, Shuai; Feng, Liang; Guo, Bingbing; Qin, Jun-Sheng; Xu, Ben; Lollar, Christina; Sun, Daofeng; Zhou, Hong-Cai

2018-04-23

Multi-component metal-organic frameworks (MOFs) with precisely controlled pore environments are highly desired owing to their potential applications in gas adsorption, separation, cooperative catalysis, and biomimetics. A series of multi-component MOFs, namely PCN-900(RE), were constructed from a combination of tetratopic porphyrinic linkers, linear linkers, and rare-earth hexanuclear clusters (RE 6 ) under the guidance of thermodynamics. These MOFs exhibit high surface areas (up to 2523 cm 2  g -1 ) and unlimited tunability by modification of metal nodes and/or linker components. Post-synthetic exchange of linear linkers and metalation of two organic linkers were realized, allowing the incorporation of a wide range of functional moieties. Two different metal sites were sequentially placed on the linear linker and the tetratopic porphyrinic linker, respectively, giving rise to an ideal platform for heterogeneous catalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessment of in vitro oxalate degradation by Lactobacillus species cultured from veterinary probiotics.

PubMed

Cho, Jenny G; Gebhart, Connie J; Furrow, Eva; Lulich, Jody P

2015-09-01

To culture Lactobacillus spp from veterinary probiotics and measure their in vitro oxalate-degrading capacity. 2 commercial veterinary probiotics containing Lactobacillus spp. Lactobacillus spp were cultured anaerobically on selective deMan, Rogosa, Sharpe agar medium and subcultured for speciation by 16S rDNA gene sequencing. Isolates were inoculated into broth containing sodium oxalate (5 mg/L) and incubated anaerobically for 72 hours. An oxalate-degrading isolate of Lactobacillus acidophilus (American Type Culture Collection [ATCC] 53544) was the positive control sample; sterile broth containing a known quantity of sodium oxalate was the negative control sample. Oxalate concentrations were detected with ion chromatography. Oxalate degradation was assessed with Dunnett tests to detect differences in mean oxalate concentration for each isolate, compared with results for the negative control. Lactobacillus acidophilus, Lactobacillus plantarum, and Lactobacillus casei or Lactobacillus zeae (too closely related to differentiate) were isolated from probiotic 1, and L plantarum was isolated from probiotic 2. Sequencing of the 16S rDNA gene confirmed 100% homology to type species. Lactobacillus acidophilus (ATCC 53544) and L acidophilus from probiotic 1 significantly decreased oxalate concentrations by 85.3 and 161.9 mg/L, respectively. Lactobacillus plantarum from probiotics 1 and 2 significantly increased oxalate concentrations by 56.1 and 36.1 mg/L, respectively. Lactobacillus casei did not alter oxalate concentrations. Lactobacillus acidophilus isolates significantly reduced oxalate concentrations. In vivo studies are needed to determine whether probiotics containing L acidophilus decrease urine oxalate concentrations and reduce risk of urolith recurrence in dogs with a history of calcium oxalate urolithiasis.

Pentadienyl chemistry of the heavy alkaline-earth metals revisited.

PubMed

Reiners, Matthias; Fecker, Ann Christin; Freytag, Matthias; Jones, Peter G; Walter, Marc D

2014-05-14

Open-metallocenes of the heavy alkaline-earth metals [(η(5)-Pdl')2M(thf)n] (M = Ca (1), Sr (2), n = 1; M = Ba (3), n = 2; Pdl' = 2,4-tBu2C5H5) are readily prepared by salt-metathesis between MI2 and KPdl' and characterized by NMR spectroscopy and X-ray diffraction studies.

Computational Studies of Thermodynamics and Kinetics of Metal Oxides in Li-Ion Batteries and Earth's Lower Mantle Materials

NASA Astrophysics Data System (ADS)

Xu, Shenzhen

Metal oxide materials are ubiquitous in nature and in our daily lives. For example, the Earth's mantle layer that makes up about 80% of our Earth's volume is composed of metal oxide materials, the cathode materials in the lithium-ion batteries that provide power for most of our mobile electronic devices are composed of metal oxides, the chemical components of the passivation layers on many kinds of metal materials that protect the metal from further corrosion are metal oxides. This thesis is composed of two major topics about the metal oxide materials in nature. The first topic is about our computational study of the iron chemistry in the Earth's lower mantle metal oxide materials, i.e. the bridgmanite (Fe-bearing MgSiO3 where iron is the substitution impurity element) and the ferropericlase (Fe-bearing MgO where iron is the substitution impurity element). The second topic is about our multiscale modeling works for understanding the nanoscale kinetic and thermodynamic properties of the metal oxide cathode interfaces in Li-ion batteries, including the intrinsic cathode interfaces (intergrowth of multiple types of cathode materials, compositional gradient cathode materials, etc.), the cathode/coating interface systems and the cathode/electrolyte interface systems. This thesis uses models based on density functional theory quantum mechanical calculations to explore the underlying physics behind several types of metal oxide materials existing in the interior of the Earth or used in the applications of lithium-ion batteries. The exploration of this physics can help us better understand the geochemical and seismic properties of our Earth and inspire us to engineer the next generation of electrochemical technologies.

Influence of oxalate ligand functionalization on Co/ZSM-5 activity in Fischer Tropsch synthesis and hydrodeoxygenation of oleic acid into hydrocarbon fuels.

PubMed

Ayodele, Olumide Bolarinwa

2017-08-30

Achieving high degree of active metal dispersions at the highest possible metal loading and high reducibility of the metal remains a challenge in Fischer Tropsch synthesis (FTS) as well as in hydrogeoxygenation (HDO).This study therefore reports the influence of oxalic acid (OxA) functionalization on the metal dispersion, reducibility and activity of Co supported ZSM-5 catalyst in FTS and HDO of oleic acid into paraffin biofuel. The Brunauer-Emmett-Teller (BET) results showed that cobalt oxalate supported ZSM-5 catalyst (CoOx/ZSM-5) synthesized from the incorporation of freshly prepared cobalt oxalate complex into ZSM-5 displayed increase in surface area, pore volume and average pore size while the nonfunctionalized cobalt supported on ZSM-5 (Co/ZSM-5) catalyst showed reduction in those properties. Furthermore, both XRD and XPS confirmed the presence of Co° formed from the decomposition of CoOx during calcination of CoOx/ZSM-5 under inert atmosphere. The HRTEM showed that Co species average particle sizes were smaller in CoOx/ZSM-5 than in Co/ZSM-5, and in addition, CoOx/ZSM-5 shows a clear higher degree of active metal dispersion. The FTS result showed that at CO conversion over Co/ZSM-5 and CoOx/ZSM-5 catalysts were 74.28% and 94.23% and their selectivity to C 5+ HC production were 63.15% and 75.4%, respectively at 4 h TOS. The HDO result also showed that the CoOx/ZSM-5 has higher OA conversion of 92% compared to 59% over Co/ZSM-5. In addition CoOx/ZSM-5 showed higher HDO and isomerization activities compared to Co/ZSM-5.

NALP3-mediated inflammation is a principal cause of progressive renal failure in oxalate nephropathy

PubMed Central

Knauf, Felix; Asplin, John R.; Granja, Ignacio; Schmidt, Insa M.; Moeckel, Gilbert; David, Rachel; Flavell, Richard A.; Aronson, Peter S.

2013-01-01

Oxalate nephropathy with renal failure is caused by multiple disorders causing hyperoxaluria due to either overproduction of oxalate (primary hyperoxaluria) or excessive absorption of dietary oxalate (enteric hyperoxaluria). To study the etiology of renal failure in crystal-induced kidney disease, we created a model of progressive oxalate nephropathy by feeding mice a diet high in soluble oxalate (high oxalate in the absence of dietary calcium). Renal histology was characterized by intratubular calcium-oxalate crystal deposition with an inflammatory response in the surrounding interstitium. Oxalate nephropathy was not found in mice fed a high oxalate diet that also contained calcium. NALP3, also known as cryopyrin, has been implicated in crystal-associated diseases such as gout and silicosis. Mice fed the diet high in soluble oxalate demonstrated increased NALP3 expression in the kidney. Nalp3-null mice were completely protected from the progressive renal failure and death that occurred in wild-type mice fed the diet high in soluble oxalate. NALP3-deficiency did not affect oxalate homeostasis, thereby excluding differences in intestinal oxalate handling to explain the observed phenotype. Thus, progressive renal failure in oxalate nephropathy results primarily from NALP3-mediated inflammation. PMID:23739234

Effect of rare earth metal on the spin-orbit torque in magnetic heterostructures

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

Ueda, Kohei; Pai, Chi-Feng; Tan, Aik Jun

2016-06-06

We report the effect of the rare earth metal Gd on current-induced spin-orbit torques (SOTs) in perpendicularly magnetized Pt/Co/Gd heterostructures, characterized using harmonic measurements and spin-torque ferromagnetic resonance (ST-FMR). By varying the Gd metal layer thickness from 0 nm to 8 nm, harmonic measurements reveal a significant enhancement of the effective fields generated from the Slonczewski-like and field-like torques. ST-FMR measurements confirm an enhanced effective spin Hall angle and show a corresponding increase in the magnetic damping constant with increasing Gd thickness. These results suggest that Gd plays an active role in generating SOTs in these heterostructures. Our finding may lead tomore » spin-orbitronics device application such as non-volatile magnetic random access memory, based on rare earth metals.« less

Theoretical Study of pKa Values for Trivalent Rare-Earth Metal Cations in Aqueous Solution.

PubMed

Yu, Donghai; Du, Ruobing; Xiao, Ji-Chang; Xu, Shengming; Rong, Chunying; Liu, Shubin

2018-01-18

Molecular acidity of trivalent rare-earth metal cations in aqueous solution is an important factor dedicated to the efficiency of their extraction and separation processes. In this work, the aqueous acidity of these metal ions has been quantitatively investigated using a few theoretical approaches. Our computational results expressed in terms of pK a values agree well with the tetrad effect of trivalent rare-earth ions extensively reported in the extraction and separation of these elements. Strong linear relationships have been observed between the acidity and quantum electronic descriptors such as the molecular electrostatic potential on the acidic nucleus and the sum of the valence natural atomic orbitals energies of the dissociating proton. Making use of the predicted pK a values, we have also predicted the major ionic forms of these species in the aqueous environment with different pH values, which can be employed to rationalize the behavior difference of different rare-earth metal cations during the extraction process. Our present results should provide needed insights not only for the qualitatively understanding about the extraction and separation between yttrium and lanthanide elements but also for the prediction of novel and more efficient rare-earth metal extractants in the future.

MRP-1 and BCRP Promote the Externalization of Phosphatidylserine in Oxalate-treated Renal Epithelial Cells: Implications for Calcium Oxalate Urolithiasis.

PubMed

Li, YiFu; Yu, ShiLiang; Gan, XiuGuo; Zhang, Ze; Wang, Yan; Wang, YingWei; An, RuiHua

2017-09-01

To investigate the possible involvement of multidrug resistance-associated protein 1 (MRP-1) and breast cancer resistance protein (BCRP) in the oxalate-induced redistribution of phosphatidylserine (PS) in renal epithelial cell membranes. A western blot analysis was used to examine the MRP-1 and BCRP expression levels. Surface-expressed PS was detected by the annexin V-binding assay. The cell-permeable fluorogenic probe 2,7-dichlorofluorescein diacetate was used to measure the intracellular reactive oxygen species (ROS) level. A rat model of hyperoxaluria was obtained using 0.5% ethylene glycol and 1.0% ammonium chloride. In addition, certain animals received verapamil (50 mg/kg body weight), which is a common inhibitor of MRP-1 and BCRP. The degree of nephrolithiasis was assessed histomorphometrically using sections stained by Pizzolato method and by measuring the calcium oxalate crystal content in the renal tissue. Oxalate produced a concentration-dependent increase in the synthesis of MRP-1 and BCRP. Treatment with MK571 and Ko143 (MRP-1- and BCRP-specific inhibitors, respectively) significantly attenuated the oxalate-induced PS externalization. Adding the antioxidant N-acetyl-l-cysteine significantly reduced MRP-1 and BCRP expression. In vivo, markedly decreased nephrocalcinosis was observed compared with that in the rat model of hyperoxaluria without verapamil treatment. Oxalate induces the upregulation of MRP-1 and BCRP, which act as phospholipid floppases causing PS externalization in the renal epithelial cell membrane. The process is mediated by intracellular ROS production. The ROS-mediated increase in the synthesis of MRP-1 and BCRP can play an important role in hyperoxaluria-promoted calcium oxalate urolithiasis by facilitating phosphatidylserine redistribution in renal epithelial cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Theoretical study of the alkaline-earth metal superoxides BeO2 through SrO2

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Sodupe, Mariona; Langhoff, Stephen R.

1992-01-01

Three competing bonding mechanisms have been identified for the alkaline-earth metal superoxides: these result in a change in the optimal structure and ground state as the alkaline-earth metal becomes heavier. For example, BeO2 has a linear 3Sigma(-)g ground-state structure, whereas both CaO2 and SrO2 have C(2v)1A1 structures. For MgO2, the theoretical calculations are less definitive, as the 3A2 C(2v) structure is computed to lie only about 3 kcal/mol above the 3Sigma(-)g linear structure. The bond dissociation energies for the alkaline-earth metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional or coupled-cluster singles and doubles level with a perturbational estimate of the triple excitations.

Alkaline earth metal doped tin oxide as a novel oxygen storage material

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

Dong, Qiang, E-mail: dong@tagen.tohoku.ac.jp; Yin, Shu; Yoshida, Mizuki

2015-09-15

Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tinmore » oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.« less

Aluminum Citrate Prevents Renal Injury from Calcium Oxalate Crystal Deposition

PubMed Central

Besenhofer, Lauren M.; Cain, Marie C.; Dunning, Cody

2012-01-01

Calcium oxalate monohydrate crystals are responsible for the kidney injury associated with exposure to ethylene glycol or severe hyperoxaluria. Current treatment strategies target the formation of calcium oxalate but not its interaction with kidney tissue. Because aluminum citrate blocks calcium oxalate binding and toxicity in human kidney cells, it may provide a different therapeutic approach to calcium oxalate-induced injury. Here, we tested the effects of aluminum citrate and sodium citrate in a Wistar rat model of acute high-dose ethylene glycol exposure. Aluminum citrate, but not sodium citrate, attenuated increases in urea nitrogen, creatinine, and the ratio of kidney to body weight in ethylene glycol–treated rats. Compared with ethylene glycol alone, the addition of aluminum citrate significantly increased the urinary excretion of both crystalline calcium and crystalline oxalate and decreased the deposition of crystals in renal tissue. In vitro, aluminum citrate interacted directly with oxalate crystals to inhibit their uptake by proximal tubule cells. These results suggest that treating with aluminum citrate attenuates renal injury in rats with severe ethylene glycol toxicity, apparently by inhibiting calcium oxalate’s interaction with, and retention by, the kidney epithelium. PMID:23138489

Evidence for a cytoplasmic pathway of oxalate biosynthesis in Aspergillus niger

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

Kubicek, C.P.; Schreferl-Kunar, G.; Woehrer, W.

1988-03-01

Oxalate accumulation of up to 8 g/liter was induced in Aspergillus niger by shifting the pH from 6 to 8. This required the presence of P/sub i/ and a nitrogen source and was inhibited by the protein synthesis inhibitor cycloheximide. Exogenously added /sup 14/CO/sub 2/ was not incorporated into oxalate, but was incorporated into acetate and malate, thus indicating the biosynthesis of oxalate by hydrolytic cleavage of oxaloacetate. Inhibition of mitochondrial citrate metabolism by fluorocitrate did not significantly decrease the oxalate yield. The putative enzyme that was responsible for this oxaloacetate hydrolase (EC 3.7.1.1), which was induced de novo duringmore » the pH shift. Subcellular fractionation of oxalic acid-forming mycelia of A. niger showed that this enzyme is located in the cytoplasm of A. niger. The results are consistent with a cytoplasmic pathway of oxalate formation which does not involve the tricarboxylic acid cycle.« less

Blending Non-Group-3 Transition Metal and Rare-Earth Metal into a C80 Fullerene Cage with D5h Symmetry.

PubMed

Wei, Tao; Jin, Fei; Guan, Runnan; Huang, Jing; Chen, Muqing; Li, Qunxiang; Yang, Shangfeng

2018-02-11

Rare-earth metals have been mostly entrapped into fullerene cages to form endohedral clusterfullerenes, whereas non-Group-3 transition metals that can form clusterfullerenes are limited to titanium (Ti) and vanadium (V), and both are exclusively entrapped within an I h -C 80 cage. Non-Group-3 transition-metal-containing endohedral fullerenes based on a C 80 cage with D 5h symmetry, V x Sc 3-x N@D 5h -C 80 (x=1, 2), have now been synthesized, which exhibit two variable cluster compositions. The molecular structure of VSc 2 N@D 5h -C 80 was unambiguously determined by X-ray crystallography. According to a comparative study with the reported Ti- and V-containing clusterfullerenes based on a I h -C 80 cage and the analogous D 5h -C 80 -based metal nitride clusterfullerenes containing rare-earth metals only, the decisive role of the non-Group-3 transition metal on the formation of the corresponding D 5h -C 80 -based clusterfullerenes is unraveled. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

LAB-SCALE DEMONSTRATION OF PLUTONIUM PURIFICATION BY ANION EXCHANGE, PLUTONIUM (IV) OXALATE PRECIPITATION, AND CALCINATION TO PLUTONIUM OXIDE TO SUPPORT THE MOX FEED MISSION

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

Crowder, M.; Pierce, R.

2012-08-22

H-Canyon and HB-Line are tasked with the production of PuO{sub 2} from a feed of plutonium metal. The PuO{sub 2} will provide feed material for the MOX Fuel Fabrication Facility. After dissolution of the Pu metal in H-Canyon, the solution will be transferred to HB-Line for purification by anion exchange. Subsequent unit operations include Pu(IV) oxalate precipitation, filtration and calcination to form PuO{sub 2}. This report details the results from SRNL anion exchange, precipitation, filtration, calcination, and characterization tests, as requested by HB-Line1 and described in the task plan. This study involved an 80-g batch of Pu and employed testmore » conditions prototypical of HB-Line conditions, wherever feasible. In addition, this study integrated lessons learned from earlier anion exchange and precipitation and calcination studies. H-Area Engineering selected direct strike Pu(IV) oxalate precipitation to produce a more dense PuO{sub 2} product than expected from Pu(III) oxalate precipitation. One benefit of the Pu(IV) approach is that it eliminates the need for reduction by ascorbic acid. The proposed HB-Line precipitation process involves a digestion time of 5 minutes after the time (44 min) required for oxalic acid addition. These were the conditions during HB-line production of neptunium oxide (NpO{sub 2}). In addition, a series of small Pu(IV) oxalate precipitation tests with different digestion times were conducted to better understand the effect of digestion time on particle size, filtration efficiency and other factors. To test the recommended process conditions, researchers performed two nearly-identical larger-scale precipitation and calcination tests. The calcined batches of PuO{sub 2} were characterized for density, specific surface area (SSA), particle size, moisture content, and impurities. Because the 3013 Standard requires that the calcination (or stabilization) process eliminate organics, characterization of PuO{sub 2} batches monitored

High-pressure metallization of FeO and implications for the earth's core

NASA Technical Reports Server (NTRS)

Knittle, Elise; Jeanloz, Raymond

1986-01-01

The phase diagram of FeO has been experimentally determined to pressures of 155 GPa and temperatures of 4000 K using shock-wave and diamond-cell techniques. A metallic phase of FeO is observed at pressures greater than 70 GPa and temperatures exceeding 1000 K. The metallization of FeO at high pressures implies that oxygen can be present as the light alloying element of the earth's outer core, in accord with the geochemical predictions of Ringwood (1977 and 1979). The high pressures necessary for this metallization suggest that the core has acquired its composition well after the initial stages of the earth's accretion. Direct experimental observations at elevated pressures and temperatures indicate that core-forming alloy can react chemically with oxides such as those forming the mantle. The core and mantle may never have reached complete chemical equilibrium, however. If this is the case, the core-mantle boundary is likely to be a zone of active chemical reactions.

Net Intestinal Transport of Oxalate Reflects Passive Absorption and SLC26A6-mediated Secretion

PubMed Central

Knauf, Felix; Ko, Narae; Jiang, Zhirong; Robertson, William G.; Van Itallie, Christina M.; Anderson, James M.

2011-01-01

Mice lacking the oxalate transporter SLC26A6 develop hyperoxalemia, hyperoxaluria, and calcium-oxalate stones as a result of a defect in intestinal oxalate secretion, but what accounts for the absorptive oxalate flux remains unknown. We measured transepithelial absorption of [14C]oxalate simultaneously with the flux of [3H]mannitol, a marker of the paracellular pathway, across intestine from wild-type and Slc26a6-null mice. We used the anion transport inhibitor DIDS to investigate other members of the SLC26 family that may mediate transcellular oxalate absorption. Absorptive flux of oxalate in duodenum was similar to mannitol, insensitive to DIDS, and nonsaturable, indicating that it is predominantly passive and paracellular. In contrast, in wild-type mice, secretory flux of oxalate in duodenum exceeded that of mannitol, was sensitive to DIDS, and saturable, indicating transcellular secretion of oxalate. In Slc26a6-null mice, secretory flux of oxalate was similar to mannitol, and no net flux of oxalate occurred. Absorptive fluxes of both oxalate and mannitol varied in parallel in different segments of small and large intestine. In epithelial cell lines, modulation of the charge selectivity of the claudin-based pore pathway did not affect oxalate permeability, but knockdown of the tight-junction protein ZO-1 enhanced permeability to oxalate and mannitol in parallel. Moreover, formation of soluble complexes with cations did not affect oxalate absorption. In conclusion, absorptive oxalate flux occurs through the paracellular “leak” pathway, and net absorption of dietary oxalate depends on the relative balance between absorption and SLC26A6-dependent transcellular secretion. PMID:22021714

Urine oxalate biological variation in patients with primary hyperoxaluria.

PubMed

Clifford-Mobley, Oliver; Sjögren, Anna; Lindner, Elisabeth; Rumsby, Gill

2016-08-01

Hyperoxaluria is a well-recognised risk factor for urolithiasis and patients with primary hyperoxaluria (PH) gradually build up calcium oxalate deposits leading to chronic kidney disease. Efforts to improve treatment for PH have focused on reducing urine oxalate excretion and thus decreasing lithogenesis. To determine the efficacy of treatments designed to alter a biochemical parameter it is necessary to know the biological and analytical variation of that parameter. In this study, we estimated the intra-individual biological variation of urine oxalate excretion in patients with PH, and from this determined what would constitute a significant change in the form of a reference change value (RCV). Each patient collected four 24-h urines on consecutive weeks. The intra-individual biological variation of oxalate excretion calculated from these samples ranged from 0 to 36 % with a mean of 14 %. The corresponding RCVs were 4-84 % with a mean of 32 %. This result implies that, on average, a reduction of almost one-third in urine oxalate excretion is required to prove an effect from treatment. The wide range of biological variation between individuals may reflect other, as yet unknown, determinants of oxaluria in PH, as well as inaccuracies in urine collection. The data suggest that it is more appropriate to use individual RCVs established prior to treatment to determine its efficacy: a relatively small fall in urine oxalate excretion may be outside the biological variation of some patients but not of others.

Modulation of polyepoxysuccinic acid on crystallization of calcium oxalate

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

Zhang, Yanqing; Tang, Yongming, E-mail: tangym@njtech.edu.cn; Xu, Jinqiu

The influence of polyepoxysuccinic acid (PESA) on the phase composition and crystal morphology of calcium oxalate was investigated in this paper. It was found that the presence of PESA inhibited the growth of the monoclinic calcium oxalate monohydrate (COM) crystal and promoted the nucleation of the tetragonal calcium oxalate dihydrate (COD). In addition, with the increase in PESA concentration, the aggregation of COD crystals was reduced but the particle size was increased. Under the conditions of low calcium-to-oxalate ratio and high CaOx concentration, PESA could not effectively stabilize the formation of COD. Based on molecular dynamic simulations, the adsorption ofmore » PESA on CaOx crystal faces was confirmed. - Graphical abstract: Introduction of PESA into crystallization solutions promotes the formation of calcium oxalate dehydrate and modifies the morphology of crystals. - Highlights: • PESA induces the formation of COD at low supersaturation. • Establishment of Ca-rich surface augments the adsorption of PESA. • At Ca/Ox=0.5 PESA cannot induce the formation of COD compared with Ca/Ox=2. • Interaction of PESA with COM faces is stronger than that with COD faces.« less

Total, Soluble and Insoluble Oxalate Contents of Ripe Green and Golden Kiwifruit.

PubMed

Nguyễn, Hà Vũ Hồng; Savage, Geoffrey P

2013-03-05

Three bulk samples of two different cultivars of kiwifruit, green ( Actinidia deliciosa L . ) and golden ( Actinidia chinensis L . ) were bought ripe, ready to eat from a local market. The aim of the study was to determine the oxalate composition of each of the three fractions of kiwifruit, namely skin, pulp and seeds. The pulp consisted of 90.4% of the edible portion of the two cultivars while the skin and seeds made up a mean of 8.0% and 1.6% respectively. Total oxalate was extracted with 2.0 M HCL at 21 °C for 15 min and soluble oxalates extracted at 21 °C in water for 15 min from each fraction. The total and soluble oxalate compositions of each fraction were determined using ion exchange HPLC chromatography. The pulp of golden kiwifruit contained lower amounts of total oxalates (15.7 vs. 19.3 mg/100 g FW) and higher amounts of soluble oxalates (8.5 vs. 7.6 mg/100 g FW) when compared to the green cultivar. The skin of the green cultivar contained lower levels of insoluble oxalates (36.9 vs. 43.6 mg/100 g FW), while the seeds of the green cultivar contained higher levels of insoluble oxalates 106.7 vs. 84.7 mg/100 g FW.

A new series of mixed oxalates MM'(C 2O 4) 3(H 2O) 3· nH 2O (M = Cd, Hg, Pb; M' = Zr, Hf) based on eight-fold coordinated metals: Synthesis, crystal structure from single-crystal and powder diffraction data and thermal behaviour

NASA Astrophysics Data System (ADS)

Gavilan, Elisabeth; Audebrand, Nathalie; Jeanneau, Erwann

2007-11-01

A new series of mixed oxalates MM'(C 2O 4) 3(H 2O) 3· nH 2O (M = Cd, Hg, Pb; M' = Zr, Hf) has been prepared. The crystal structures have been solved from single-crystal and powder diffraction data. The isotypical compounds crystallise with space group P2 1/ c (No. 14). The structures consist of honeycomb layers formed by eight-fold coordinated metals, in a distorted square-based antiprismatic conformation, connected together via oxalates which act as bidentate ligands and also as monodentate in a less-common μ3-bridging mode. Sheets are built from two shifted honeycomb layers and linked to each other through a hydrogen network. The resulting frameworks of the series display a compact two-dimensional arrangement of polyhedra MO 8 and M'O 8. Weakly-bonded water molecules are located between and within the sheets. Comparisons with the 3D open-framework structures of related metal oxalates are made. The dehydration processes occur in three or four steps. The final products are MO, M'O 2 and PbZrO 3 resulting from the sublimation of PbO in air. The size of PbZrO 3 crystallites, which are on average isotropic, has been evaluated to be 1055 Å from line-broadening analysis.

Externalization of phosphatidylserine via multidrug resistance 1 (MDR1)/P-glycoprotein in oxalate-treated renal epithelial cells: implications for calcium oxalate urolithiasis.

PubMed

Li, Yu-Hang; Yu, Shi-Liang; Gan, Xiu-Guo; Pan, Shang-Ha; Teng, Yue-Qiu; An, Rui-Hua

2016-02-01

We investigated the possible involvement of multidrug resistance protein 1 P-glycoprotein (MDR1 P-gp) in the oxalate-induced redistribution of phosphatidylserine in renal epithelial cell membranes. Real-time PCR and western blotting were used to examine MDR1 expression in Madin-Darby canine kidney cells at the mRNA and protein levels, respectively, whereas surface-expressed phosphatidylserine was detected by the annexin V-binding assay. Oxalate treatment resulted in increased synthesis of MDR1, which resulted in phosphatidylserine (PS) externalization in the renal epithelial cell membrane. Treatment with the MDR1 inhibitor PSC833 significantly attenuated phosphatidylserine externalization. Transfection of the human MDR1 gene into renal epithelial cells significantly increased PS externalization. To our knowledge, this study is the first to show that oxalate increases the synthesis of MDR1 P-gp, which plays a key role in hyperoxaluria-promoted calcium oxalate urolithiasis by facilitating phosphatidylserine redistribution in renal epithelial cells.

Unusual calcium oxalate crystals in ethylene glycol poisoning.

PubMed

Godolphin, W; Meagher, E P; Sanders, H D; Frohlich, J

1980-06-01

A patient poisoned with ethylene glycol exhibited the symptoms of (1) hysteria, (2) metabolic acidosis with both a large anion gap and osmolal gap, and (3) crystalluria. However, the shape of the urinary crystals was prismatic and resembled hippurate rather than the expected dipyramidal calcium oxalate dihydrate. X-ray crystallography positively identified them as calcium oxalate monohydrate.

Crystallization of calcium oxalate in minimally diluted urine

NASA Astrophysics Data System (ADS)

Bretherton, T.; Rodgers, A.

1998-09-01

Crystallization of calcium oxalate was studied in minimally diluted (92%) urine using a mixed suspension mixed product crystallizer in series with a Malvern particle sizer. The crystallization was initiated by constant flow of aqueous sodium oxalate and urine into the reaction vessel via two independent feed lines. Because the Malvern cell was in series with the reaction vessel, noninvasive measurement of particle sizes could be effected. In addition, aliquots of the mixed suspension were withdrawn and transferred to a Coulter counter for crystal counting and sizing. Steady-state particle size distributions were used to determine nucleation and growth kinetics while scanning electron microscopy was used to examine deposited crystals. Two sets of experiments were performed. In the first, the effect of the concentration of the exogenous sodium oxalate was investigated while in the second, the effect of temperature was studied. Calcium oxalate nucleation and growth rates were found to be dependent on supersaturation levels inside the crystallizer. However, while growth rate increased with increasing temperature, nucleation rates decreased. The favored phases were the trihydrate at 18°C, the dihydrate at 38° and the monohydrate at 58°C. The results of both experiments are in agreement with those obtained in other studies that have been conducted in synthetic and in maximally diluted urine and which have employed invasive crystal counting and sizing techniques. As such, the present study lends confidence to the models of urinary calcium oxalate crystallization processes which currently prevail in the literature.

A simple method for quantitating the propensity for calcium oxalate crystallization in urine

NASA Technical Reports Server (NTRS)

Wabner, C. L.; Pak, C. Y.

1991-01-01

To assess the propensity for spontaneous crystallization of calcium oxalate in urine, the permissible increment in oxalate is calculated. The previous method required visual observation of crystallization with the addition of oxalate, this warranted the need for a large volume of urine and a sacrifice in accuracy in defining differences between small incremental changes of added oxalate. Therefore, this method has been miniaturized and spontaneous crystallization is detected from the depletion of radioactive oxalate. The new "micro" method demonstrated a marked decrease (p < 0.001) in the permissible increment in oxalate in urine of stone formers versus normal subjects. Moreover, crystallization inhibitors added to urine, in vitro (heparin or diphosphonate) or in vivo (potassium citrate administration), substantially increased the permissible increment in oxalate. Thus, the "micro" method has proven reliable and accurate in discriminating stone forming from control urine and in distinguishing changes of inhibitory activity.

Microbiota Diversification and Crash Induced by Dietary Oxalate in the Mammalian Herbivore Neotoma albigula

PubMed Central

Dale, Colin; Dearing, M. Denise

2017-01-01

ABSTRACT Oxalate, broadly found in both dietary and endogenous sources, is a primary constituent in 80% of kidney stones, an affliction that has tripled in prevalence over the last 40 years. Oxalate-degrading bacteria within the gut microbiota can mitigate the effects of oxalate and are negatively correlated with kidney stone formation, but bacteriotherapies involving oxalate-degrading bacteria have met with mixed results. To inform the development of more effective and consistent bacteriotherapies, we sought to quantify the interactions and limits between oxalate and an oxalate-adapted microbiota from the wild mammalian herbivore Neotoma albigula (woodrat), which consumes a high-oxalate diet in the wild. We tracked the microbiota over a variable-oxalate diet ranging from 0.2% to 12%, with the upper limit approximating 10× the level of human consumption. The N. albigula microbiota was capable of degrading ~100% of dietary oxalate regardless of the amount consumed. However, the microbiota exhibited significant changes in diversity dynamically at the operational taxonomic unit (OTU), family, and community levels in accordance with oxalate input. Furthermore, a cohesive microbial network was stimulated by the consumption of oxalate and exhibited some resistance to the effects of prolonged exposure. This study demonstrates that the oxalate-adapted microbiota of N. albigula exhibits a very high level of degradation and tolerance for oxalate. IMPORTANCE The bacteria associated with mammalian hosts exhibit extensive interactions with overall host physiology and contribute significantly to the health of the host. Bacteria are vital to the mitigation of the toxic effects of oxalate specifically as mammals do not possess the enzymes to degrade this compound, which is present in the majority of kidney stones. Contrary to the body of literature on a few oxalate-degrading specialists, our work illustrates that oxalate stimulates a broad but cohesive microbial network in a

Correlation between oxalic acid production and copper tolerance in Wolfiporia cocos

Treesearch

C. A. Clausen; Frederick Green; B. M. Woodward; J. W. Evans; R. C. DeGroot

2000-01-01

The increased interest in copper-based wood preservatives has hastened the need for understanding why some fungi are able to attack copper-treated wood. Due in part to accumulation of oxalic acid by brown-rot fungi and visualization of copper oxalate crystals in wood decayed by known copper-tolerant decay fungi, oxalic acid has been implicated in copper tolerance by...

Experimentally determined Si isotope fractionation between silicate and Fe metal and implications for Earth's core formation

NASA Astrophysics Data System (ADS)

Shahar, Anat; Ziegler, Karen; Young, Edward D.; Ricolleau, Angele; Schauble, Edwin A.; Fei, Yingwei

2009-10-01

Stable isotope fractionation amongst phases comprising terrestrial planets and asteroids can be used to elucidate planet-forming processes. To date, the composition of the Earth's core remains largely unknown though cosmochemical and geophysical evidence indicates that elements lighter than iron and nickel must reside there. Silicon is often cited as a light element that could explain the seismic properties of the core. The amount of silicon in the core, if any, can be deduced from the difference in 30Si/ 28Si between meteorites and terrestrial rocks if the Si isotope fractionation between silicate and Fe-rich metal is known. Recent studies (e.g., [Georg R.B., Halliday A.N., Schauble E.A., Reynolds B.C., 2007. Silicon in the Earth's core. Nature 447 (31), 1102-1106.]; [Fitoussi, C., Bourdon, B., Kleine, T., Oberli, F., Reynolds, B. C., 2009. Si isotope systematics of meteorites and terrestrial peridotites: implications for Mg/Si fractionation in the solar nebula and for Si in the Earth's core. Earth Planet. Sci. Lett. 287, 77-85.]) showing (sometimes subtle) differences between 30Si/ 28Si in meteorites and terrestrial rocks suggest that Si missing from terrestrial rocks might be in the core. However, any conclusion based on Earth-meteorite comparisons depends on the veracity of the 30Si/ 28Si fractionation factor between silicates and metals at appropriate conditions. Here we present the first direct experimental evidence that silicon isotopes are not distributed uniformly between iron metal and rock when equilibrated at high temperatures. High-precision measurements of the silicon isotope ratios in iron-silicon alloy and silicate equilibrated at 1 GPa and 1800 °C show that Si in silicate has higher 30Si/ 28Si than Si in metal, by at least 2.0‰. These findings provide an experimental foundation for using isotope ratios of silicon as indicators of terrestrial planet formation processes. They imply that if Si isotope equilibrium existed during segregation of Earth

Effect of Dietary Oxalate on the Gut Microbiota of the Mammalian Herbivore Neotoma albigula

PubMed Central

Oakeson, Kelly F.; Dale, Colin; Dearing, M. Denise

2016-01-01

Diet is one of the primary drivers that sculpts the form and function of the mammalian gut microbiota. However, the enormous taxonomic and metabolic diversity held within the gut microbiota makes it difficult to isolate specific diet-microbe interactions. The objective of the current study was to elucidate interactions between the gut microbiota of the mammalian herbivore Neotoma albigula and dietary oxalate, a plant secondary compound (PSC) degraded exclusively by the gut microbiota. We quantified oxalate degradation in N. albigula fed increasing amounts of oxalate over time and tracked the response of the fecal microbiota using high-throughput sequencing. The amount of oxalate degraded in vivo was linearly correlated with the amount of oxalate consumed. The addition of dietary oxalate was found to impact microbial species diversity by increasing the representation of certain taxa, some of which are known to be capable of degrading oxalate (e.g., Oxalobacter spp.). Furthermore, the relative abundances of 117 operational taxonomic units (OTU) exhibited a significant correlation with oxalate consumption. The results of this study indicate that dietary oxalate induces complex interactions within the gut microbiota that include an increase in the relative abundance of a community of bacteria that may contribute either directly or indirectly to oxalate degradation in mammalian herbivores. PMID:26896138

Composite nanoparticles containing rare earth metal and methods of preparation thereof

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

Kandapallil, Binil Itty Ipe; Krishnan, Lakshmi; Johnson, Francis

The present invention is directed to composite nanoparticles comprising a metal, a rare earth element, and, optionally, a complexing ligand. The invention is also directed to composite nanoparticles having a core-shell structure and to processes for preparation of composite nanoparticles of the invention.

Marsh plant response to metals: Exudation of aliphatic low molecular weight organic acids (ALMWOAs)

NASA Astrophysics Data System (ADS)

Rocha, A. Cristina S.; Almeida, C. Marisa R.; Basto, M. Clara P.; Vasconcelos, M. Teresa S. D.

2016-03-01

Metal exposure is known to induce the production and secretion of substances, such as aliphatic low molecular weight organic acids (ALMWOAs), into the rhizosphere by plant roots. Knowledge on this matter is extensive for soil plants but still considerably scarce regarding marsh plants roots adapted to high salinity media. Phragmites australis and Halimione portulacoides, two marsh plants commonly distributed in European estuarine salt marshes, were used to assess the response of roots of both species, in terms of ALMWOAs exudation, to Cu, Ni and Cd exposure (isolated and in mixture since in natural environment, they are exposed to mixture of metals). As previous studies were carried out in unrealistic and synthetic media, here a more natural medium was selected. Therefore, in vitro experiments were carried out, with specimens of both marsh plants, and in freshwater contaminated with two different Cu, Ni and Cd concentrations (individual metal and in mixture). Both marsh plants were capable of liberating ALMWOAs into the surrounding medium. Oxalic, citric and maleic acids were found in P. australis root exudate solutions and oxalic and maleic acids in H. portulacoides root exudate solutions. ALMWOA liberation by both plants was plant species and metal-dependent. For instance, Cu affected the exudation of oxalic acid by H. portulacoides and of oxalic and citric acids by P. australis roots. In contrast, Ni and Cd did not stimulate any specific response. Regarding the combination of all metals, H. portulacoides showed a similar response to that observed for Cu individually. However, in the P. australis case, at high metal concentration mixture, a synergetic effect led to the increase of oxalic acid levels in root exudate solution and to a decrease of citric acid liberation. A correlation between ALMWOAs exudation and metal accumulation could not be established. P. australis and H. portulacoides are considered suitable metal phytoremediators of estuarine impacted areas

Patterns of calcium oxalate monohydrate crystallization in complex biological systems

NASA Astrophysics Data System (ADS)

Golovanova, O. A.; Korol'kov, V. V.; Kuimova, M. V.

2017-01-01

The paper presents the features of calcium oxalate crystallization in the presence of additives revealed through experimental modeling. The patterns of phase formation are shown for the Ca2+ - C2O4 2- - H2O and Ca2+ - C2O4 2- - PO4 3- - H2O systems with the components and pH of the saline varying over a wide concentrations range. The effect of additives on crystallization of calcium oxalate monohydrate was investigated. It was found that the ionic strength and magnesium ions are inhibitors, and calcium oxalate and hydroxyapatite crystals are catalysts of calcium oxalate monohydrate crystallization. The basic calcium phosphate (apatite) was found to be most thermodynamically stable, which indicates its special role in kidney stone formation since it is found in virtually all stones.

Metallic rare-earth silicide nanowires on silicon surfaces.

PubMed

Dähne, Mario; Wanke, Martina

2013-01-09

The formation, atomic structure, and electronic properties of self-assembled rare-earth silicide nanowires on silicon surfaces were studied by scanning tunneling microscopy and angle-resolved photoelectron spectroscopy. Metallic dysprosium and erbium silicide nanowires were observed on both the Si(001) and Si(557) surfaces. It was found that they consist of hexagonal rare-earth disilicides for both surface orientations. On Si(001), the nanowires are characterized by a one-dimensional band structure, while the electronic dispersion is two-dimensional for the nanowires formed on Si(557). This behavior is explained by the different orientations of the hexagonal c axis of the silicide leading to different conditions for the carrier confinement. By considering this carrier confinement it is demonstrated how the one-dimensional band structure of the nanowires on Si(001) can be derived from the two-dimensional one of the silicide monolayer on Si(111).

Oxidation of aquatic pollutants by ferrous-oxalate complexes under dark aerobic conditions.

PubMed

Lee, Jaesang; Kim, Jungwon; Choi, Wonyong

2014-06-15

This study evaluates the ability of Fe(II)-oxalate complexes for the generation of OH through oxygen reduction and the oxidative degradation of aquatic pollutants under dark aerobic conditions (i.e., with oxygen but without light). The degradation of 4-chlorophenol (4-CP) was rapid in the mixture of Fe(2+) and oxalate prepared using ultrapure water, but was absent without either Fe(2+) or oxalate. The formation of Fe(II)-oxalate complexes enables two-electron reduction of oxygen to generate H2O2 and subsequent production of OH. The significant inhibition of 4-CP degradation in the presence of H2O2 and OH scavenger confirms such mechanisms. The degradation experiments with varying [Fe(2+)], [oxalate], and initial pH demonstrated that the degradation rate depends on [Fe(II)(Ox)2(2-)], but the degree of degradation is primarily determined by [Fe(II)(Ox)2(2-)]+[Fe(II)(Ox)(0)]. Efficient degradation of diverse aquatic pollutants, especially phenolic pollutants, was observed in the Fe(II)-oxalate complexes system, wherein the oxidation efficacy was primarily correlated with the reaction rate constant between pollutant and OH. The effect of various organic ligands (oxalate, citrate, EDTA, malonate, and acetate) on the degradation kinetics of 4-CP was investigated. The highest efficiency of oxalate for the oxidative degradation is attributed to its high capability to enhance the reducing power and low reactivity with OH. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of Oxalic Acid on Apis mellifera (Hymenoptera: Apidae)

PubMed Central

Rademacher, Eva; Harz, Marika; Schneider, Saskia

2017-01-01

Oxalic acid dihydrate is used to treat varroosis of Apis mellifera. This study investigates lethal and sublethal effects of oxalic acid dihydrate on individually treated honeybees kept in cages under laboratory conditions as well as the distribution in the colony. After oral application, bee mortality occurred at relatively low concentrations (No Observed Adverse Effect Level (NOAEL) 50 µg/bee; Lowest Observed Adverse Effect Level (LOAEL) 75 µg/bee) compared to the dermal treatment (NOAEL 212.5 µg/bee; LOAEL 250 µg/bee). The dosage used in regular treatment via dermal application (circa 175 µg/bee) is below the LOAEL, referring to mortality derived in the laboratory. However, the treatment with oxalic acid dihydrate caused sublethal effects: This could be demonstrated in an increased responsiveness to water, decreased longevity and a reduction in pH-values in the digestive system and the hemolymph. The shift towards stronger acidity after treatment confirms that damage to the epithelial tissue and organs is likely to be caused by hyperacidity. The distribution of oxalic acid dihydrate within a colony was shown by macro-computed tomography; it was rapid and consistent. The increased density of the individual bee was continuous for at least 14 days after the treatment indicating the presence of oxalic acid dihydrate in the hive even long after a treatment. PMID:28783129

GADOLINIUM OXALATE SOLUBILITY MEASUREMENTS IN NITRIC ACID SOLUTIONS

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

Pierce, R. A.

2012-03-12

HB-Line will begin processing Pu solutions during FY2012 that will involve the recovery of Pu using oxalate precipitation and filtration. After the precipitation and filtration processes, the filtrate solution will be transferred from HB-Line to H-Canyon. The presence of excess oxalate and unfiltered Pu oxalate solids in these solutions create a criticality safety issue if they are sent to H-Canyon without controls in H-Canyon. One approach involves H-Canyon receiving the filtrate solution into a tank that is poisoned with soluble gadolinium (Gd). Decomposition of the oxalate will occur within a subsequent H-Canyon vessel. The receipt of excess oxalate into themore » H-Canyon receipt tanks has the potential to precipitate a portion of the Gd poison in the receipt tanks. Because the amount of Gd in solution determines the maximum amount of Pu solids that H-Canyon can receive, H-Canyon Engineering requested that SRNL determine the solubility of Gd in aqueous solutions of 4-10 M nitric acid (HNO{sub 3}), 4-12 g/L Gd, and 0.15-0.25 M oxalic acid (H{sub 2}C{sub 2}O{sub 4}) at 25 °C. The target soluble Gd concentration is 6 g/L. The data indicate that the target can be achieved above 6 M HNO{sub 3} and below 0.25 M H{sub 2}C{sub 2}O{sub 4}. At 25 °C, for 6 M HNO{sub 3}, 11 g/L and 7 g/L Gd are soluble in 0.15 M and 0.25 M H{sub 2}C{sub 2}O{sub 4}, respectively. In 4 M HNO{sub 3}, the Gd solubility drops significantly to 2.5 g/L and 0.8 g/L in 0.15 M and 0.25 M H{sub 2}C{sub 2}O{sub 4}, respectively. The solubility of Gd at 8-10 M HNO{sub 3} exceeds the solubility at 6 M HNO{sub 3}. The data for 4 M HNO{sub 3} showed good agreement with data in the literature. To achieve a target of 6 g/L soluble Gd in solution in the presence of 0.15-0.25 M oxalate, the HNO{sub 3} concentration must be maintained at or above 6 M HNO{sub 3}. The solubility of Gd in 4 M HNO{sub 3} with 0.15 M oxalate at 10 °C is about 1.5 g/L. For 6 M HNO{sub 3} with 0.15 M oxalate, the solubility of

Aspects of calcium oxalate crystallization: theory, in vitro studies, and in vivo implementation.

PubMed

Rodgers, A

1999-11-01

There are three main approaches to urolithiasis research: theory, basic science, and clinical implementation. Although each approach has yielded meaningful results, there does not appear to be complete synergy between them. This article examines these approaches as they pertain to urinary calcium oxalate crystallization processes. Theoretical calculations were performed to examine the role of oxalate concentration on calcium oxalate supersaturation. The effects of magnesium, citrate, and combinations thereof on calcium oxalate crystallization kinetics were examined in a mixed suspension, mixed product removal crystallizer. Finally, male volunteers were given supplements of calcium alone and binary combinations of calcium, magnesium, and citrate to investigate their effects on the urinary supersaturation of calcium oxalate. Calculations showed that oxalate is 23 times more potent than calcium in its effect on the supersaturation of calcium oxalate. In the in vitro experiments, magnesium and citrate reduced the growth and nucleation kinetics as well as the supersaturation. In combination, these two components were more effective than the individual components in reducing the growth rate and the supersaturation. All of the supplements favorably altered the kinetic and thermodynamic risk factors. Calcium was the most effective in reducing the urinary excretion of oxalate. Articulation of these three approaches is essential for the meaningful investigation and understanding of urolithiasis.

Sulfate and thiosulfate inhibit oxalate transport via a dPrestin (Slc26a6)-dependent mechanism in an insect model of calcium oxalate nephrolithiasis.

PubMed

Landry, Greg M; Hirata, Taku; Anderson, Jacob B; Cabrero, Pablo; Gallo, Christopher J R; Dow, Julian A T; Romero, Michael F

2016-01-15

Nephrolithiasis is one of the most common urinary tract disorders, with the majority of kidney stones composed of calcium oxalate (CaOx). Given its prevalence (US occurrence 10%), it is still poorly understood, lacking progress in identifying new therapies because of its complex etiology. Drosophila melanogaster (fruitfly) is a recently developed model of CaOx nephrolithiasis. Effects of sulfate and thiosulfate on crystal formation were investigated using the Drosophila model, as well as electrophysiological effects on both Drosophila (Slc26a5/6; dPrestin) and mouse (mSlc26a6) oxalate transporters utilizing the Xenopus laevis oocyte heterologous expression system. Results indicate that both transport thiosulfate with a much higher affinity than sulfate Additionally, both compounds were effective at decreasing CaOx crystallization when added to the diet. However, these results were not observed when compounds were applied to Malpighian tubules ex vivo. Neither compound affected CaOx crystallization in dPrestin knockdown animals, indicating a role for principal cell-specific dPrestin in luminal oxalate transport. Furthermore, thiosulfate has a higher affinity for dPrestin and mSlc26a6 compared with oxalate These data indicate that thiosulfate's ability to act as a competitive inhibitor of oxalate via dPrestin, can explain the decrease in CaOx crystallization seen in the presence of thiosulfate, but not sulfate. Overall, our findings predict that thiosulfate or oxalate-mimics may be effective as therapeutic competitive inhibitors of CaOx crystallization. Copyright © 2016 the American Physiological Society.

Comparison of hot hydroxylamine hydrochloride and oxalic acid leaching of stream sediment and coated rock samples as anomaly enhancement techniques

USGS Publications Warehouse

Filipek, L.H.; Chao, T.T.; Theobald, P.K.

1982-01-01

A hot hydroxylamine hydrochloride (H-Hxl) extraction in 25% acetic acid is compared with the commonly used oxalic acid extraction as a method of anomaly enhancement for Cu and Zn in samples from two very different metal deposits and climatic environments. Results obtained on minus-80-mesh stream sediments from an area near the Magruder massive sulfide deposit in Lincoln County, Georgia, where the climate is humid subtropical, indicate that H-Hxl enhances the anomaly for Cu by a factor of 2 and for Zn by a factor of 1.5, compared to the oxalic method. Analyses of Fe oxide-coated rock samples from outcrops overlying the North Silver Bell porphyry copper deposit near Tucson, Arizona, where the climate is semi-arid to arid, indicate that both techniques effectively outline the zones of hydrothermal alteration. The H-Hxl extraction can also perform well in high-carbonate or high-clay environments, where other workers have suggested that oxalic acid is not very effective. Therefore, the H-Hxl method is recommended for general exploration use. ?? 1982.

How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

NASA Astrophysics Data System (ADS)

Kam, K.; Lemke, K.

2014-12-01

The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with

Synthesis of unsymmetrical dimethylhydrazine oxalate from rejected liquid rocket propellant

NASA Astrophysics Data System (ADS)

Mu, Xiaogang; Yang, Jingjing; Zhang, Youzhi

2018-02-01

The rejected liquid propellant unsymmetrical dimethylhydrazine (UDMH) was converted to UDMH oxalate, which has commercial value. The UDMH oxalate structure and stability were investigated by the Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and ultraviolet-visible spectrophotometric analysis. The results indicate that UDMH oxalate has good thermal and aqueous solution stability, a melting point of 144 °C, an initial decomposition temperature of 180 °C, and a peak wavelength of UV in aqueous solution at λ = 204 nm. This disposal method of rejected UDMH is highly efficient and environmentally safe.

Determination of Oxalate Content in Herbal Remedies and Dietary Supplements Based on Plant Extracts.

PubMed

Siener, Roswitha; López-Mesas, Montserrat; Valiente, Manuel; Blanco, Francisco

2016-02-01

Lifestyle, especially diet, is a prominent risk factor that affects the formation of calcium oxalate stones. Urinary oxalate excretion is directly related to the amount of oral intake and intestinal absorption rate of oxalate. This work evaluated the possibility of increasing oxalate ingestion, which could lead to secondary hyperoxaluria, associated with the intake of herbal remedies and dietary supplements containing plant extracts. A wide variety of 17 commercially available drugs and dietary supplements were analyzed using ion chromatography. The results showed remarkable differences in oxalate contents of the extracts. Total oxalate concentrations ranged from 0.03 to 2.2 mg/g in solid samples and from 0.005 to 0.073 mg/mL in liquid samples. The selected herbal remedies and dietary supplements containing plant extracts represent only a low risk for calcium oxalate stone formers, if the recommended daily dose is not exceeded.

High-pressure phase transitions in rare earth metal thulium to 195 GPa.

PubMed

Montgomery, Jeffrey M; Samudrala, Gopi K; Tsoi, Georgiy M; Vohra, Yogesh K

2011-04-20

We have performed image plate x-ray diffraction studies on a heavy rare earth metal, thulium (Tm), in a diamond anvil cell to a pressure of 195 GPa and volume compression V/V₀ = 0.38 at room temperature. The rare earth crystal structure sequence, hcp →Sm-type→ dhcp →fcc → distorted fcc, is observed in Tm below 70 GPa with the exception of a pure fcc phase. The focus of our study is on the ultrahigh-pressure phase transition and Rietveld refinement of crystal structures in the pressure range between 70 and 195 GPa. The hexagonal hR-24 phase is seen to describe the distorted fcc phase between 70 and 124 GPa. Above 124 ± 4 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of -1.5%. The equation of state data shows rapid stiffening above the phase transition at 124 GPa and is indicative of participation of f-electrons in bonding. We compare the behavior of Tm to other heavy rare-earths and heavy actinide metals under extreme conditions of pressure.

High-pressure phase transitions in rare earth metal thulium to 195 GPa

NASA Astrophysics Data System (ADS)

Montgomery, Jeffrey M.; Samudrala, Gopi K.; Tsoi, Georgiy M.; Vohra, Yogesh K.

2011-04-01

We have performed image plate x-ray diffraction studies on a heavy rare earth metal, thulium (Tm), in a diamond anvil cell to a pressure of 195 GPa and volume compression V/Vo = 0.38 at room temperature. The rare earth crystal structure sequence, {hcp}\\to {Sm {-}type} \\to {dhcp} \\to {fcc} \\to distorted fcc, is observed in Tm below 70 GPa with the exception of a pure fcc phase. The focus of our study is on the ultrahigh-pressure phase transition and Rietveld refinement of crystal structures in the pressure range between 70 and 195 GPa. The hexagonal hR- 24 phase is seen to describe the distorted fcc phase between 70 and 124 GPa. Above 124 ± 4 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.5%. The equation of state data shows rapid stiffening above the phase transition at 124 GPa and is indicative of participation of f-electrons in bonding. We compare the behavior of Tm to other heavy rare-earths and heavy actinide metals under extreme conditions of pressure.

Dynamical Correlation In Some Liquid Alkaline Earth Metals Near Melting

NASA Astrophysics Data System (ADS)

Thakore, B. Y.; Suthar, P. H.; Khambholja, S. G.; Gajjar, P. N.; Jani, A. R.

2010-12-01

The study of dynamical variables: velocity autocorrelation function (VACF) and power spectrum of liquid alkaline earth metals (Ca, Sr, and Ba) have been presented based on the static harmonic well approximation. The effective interatomic potential for liquid metals is computed using our well recognized model potential with the exchange correlation functions due to Hartree, Taylor, Ichimaru and Utsumi, Farid et al. and Sarkar et al. It is observed that the VACF computed using Sarkar et al. gives the good agreement with available molecular dynamics simulation (MD) results [Phys Rev. B 62, 14818 (2000)]. The shoulder of the power spectrum depends upon the type of local field correlation function used.

Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

PubMed

Rout, Alok; Binnemans, Koen

2014-02-28

The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

Thermodynamic Considerations of Direct Oxygen Removal from Titanium by Utilizing the Deoxidation Capability of Rare Earth Metals

NASA Astrophysics Data System (ADS)

Okabe, Toru H.; Zheng, Chenyi; Taninouchi, Yu-ki

2018-06-01

Oxygen removal from metallic Ti is extremely difficult and, currently, there is no commercial process for effectively deoxidizing Ti or its alloys. The oxygen concentration in Ti scraps is normally higher than that in virgin metals such as in Ti sponges produced by the Kroll process. When scraps are remelted with virgin metals for producing primary ingots of Ti or its alloys, the amount of scrap that can be used is limited owing to the accumulation of oxygen impurities. Future demands of an increase in Ti production and of mitigating environmental impacts require that the amount of scrap recycled as a feed material of Ti ingots should also increase. Therefore, it is important to develop methods for removing oxygen directly from Ti scraps. In this study, we evaluated the deoxidation limit for β-Ti using Y or light rare earth metals (La, Ce, Pr, or Nd) as a deoxidant. Thermodynamic considerations suggest that extra-low-oxygen Ti, with an oxygen concentration of 100 mass ppm or less can be obtained using a molten salt equilibrating with rare earth metals. The results presented herein also indicate that methods based on molten salt electrolysis for producing rare earth metals can be utilized for effectively and directly deoxidizing Ti scraps.

Microelectrophoretic study of calcium oxalate monohydrate in macromolecular solutions

NASA Technical Reports Server (NTRS)

Curreri, P. A.; Onoda, G. Y., Jr.; Finlayson, B.

1987-01-01

Electrophoretic mobilities were measured for calcium oxalate monohydrate (COM) in solutions containing macromolecules. Two mucopolysaccharides (sodium heparin and chondroitin sulfate) and two proteins (positively charged lysozyme and negatively charged bovine serum albumin) were studied as adsorbates. The effects of pH, calcium oxalate surface charge (varied by calcium or oxalate ion activity), and citrate concentration were investigated. All four macromolecules showed evidence for adsorption. The macromolecule concentrations needed for reversing the surface charge indicated that the mucopolysaccharides have greater affinity for the COM surface than the proteins. Citrate ions at high concentrations appear to compete effectively with the negative protein for surface sites but show no evidence for competing with the positively charged protein.

The influence of scale inhibitors on calcium oxalate

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

Gill, J.S.

1999-11-01

Precipitation of calcium oxalate is a common occurrence in mammalian urinary tract deposits and in various industrial processes such as paper making, brewery fermentation, sugar evaporation, and tannin concentration. Between pH 3.5 to 4.5 the driving force for calcium oxalate precipitation increases almost by three fold. It is a complicated process to predict both the nature of a deposit and at which stage of a multi-effect evaporator a particular mineral will deposit, as this depends on temperature, pH, total solids, and kinetics of mineralization. It is quite a challenge to inhibit calcium oxalate precipitation in the pH range of 4--6.more » Al{sup 3+} ions provide excellent threshold inhibition in this pH range and can be used to augment traditional inhibitors such as polyphosphates and polycarboxylates.« less

Genomic evaluation of oxalate-degrading transgenic soybean in response to Sclerotinia sclerotiorum infection

USDA-ARS?s Scientific Manuscript database

Oxalate oxidases catalyze the degradation of oxalic acid (OA). Highly resistant transgenic soybean carrying an oxalate oxidase (OxO) gene and its susceptible parent soybean line, AC Colibri, were tested for genome-wide gene expression in response to the necrotrophic, OA producing pathogen Sclerotini...

In vitro formation of Ca-oxalates and the mineral glushinskite by fungal interaction with carbonate substrates and seawater

NASA Astrophysics Data System (ADS)

Kolo, K.; Claeys, Ph.

2005-10-01

This study investigates the in vitro formation of Ca-oxalates and glushinskite through fungal interaction with carbonate substrates and seawater as a process of biologically induced metal recycling and neo-mineral formation. The study also emphasizes the role of the substrates as metal donors. In the first experiment, thin sections prepared from dolomitic rock samples of Terwagne Formation (Carboniferous, Viséan, northern France) served as substrates. The thin sections placed in Petri dishes were exposed to fungi grown from naturally existing airborne spores. In the second experiment, fungal growth and mineral formation was monitored using only standard seawater (SSW) as a substrate. Fungal growth media consisted of a high protein/carbohydrates and sugar diet with demineralized water for irrigation. Fungal growth process reached completion under uncontrolled laboratory conditions. The newly formed minerals and textural changes caused by fungal attack on the carbonate substrates were investigated using light and scanning electron microscopy (SEM-EDX), x-ray diffraction (XRD) and Raman spectroscopy. The fungal interaction and attack on the dolomitic and seawater substrates resulted in the formation of Ca-oxalates (weddellite CaC2O4·2(H2O), whewellite (CaC2O4·(H2O)) and glushinskite MgC2O4·2(H2O) associated with the destruction of the original hard substrates and their replacement by the new minerals. Both of Ca and Mg were mobilized from the experimental substrates by fungi. This metal mobilization involved a recycling of substrate metals into newly formed minerals. The biochemical and diagenetic results of the interaction strongly marked the attacked substrates with a biological fingerprint. Such fingerprints are biomarkers of primitive life. The formation of glushinskite is of specific importance that is related, besides its importance as a biomineral bearing a recycled Mg, to the possibility of its transformation through diagenetic pathway into an Mg carbonate

Novel Applications for Oxalate-Phosphate-Amine Metal-Organic-Frameworks (OPA-MOFs): Can an Iron-Based OPA-MOF Be Used as Slow-Release Fertilizer?

PubMed

Anstoetz, Manuela; Rose, Terry J; Clark, Malcolm W; Yee, Lachlan H; Raymond, Carolyn A; Vancov, Tony

2015-01-01

A porous iron-based oxalate-phosphate-amine metal-organic framework material (OPA-MOF) was investigated as a microbially-induced slow-release nitrogen (N) and phosphorus (P) fertilizer. Seedling growth, grain yields, nutrient uptake of wheat plants, and soil dynamics in incubated soil, were investigated using OPA-MOF vs standard P (triple-superphosphate) and N (urea) fertilizers in an acidic Ferralsol at two application rates (equivalent 120 and 40 kg N ha(-1)). While urea hydrolysis in the OPA-MOF treatment was rapid, conversion of ammonium to nitrate was significantly inhibited compared to urea treatment. Reduced wheat growth in OPA-MOF treatments was not caused by N-deficiency, but by limited P-bioavailability. Two likely reasons were slow P-mobilisation from the OPA-MOF or rapid P-binding in the acid soil. P-uptake and yield in OPA-MOF treatments were significantly higher than in nil-P controls, but significantly lower than in conventionally-fertilised plants. OPA-MOF showed potential as enhanced efficiency N fertilizer. However, as P-bioavailability was insufficient to meet plant demands, further work should determine if P-availability may be enhanced in alkaline soils, or whether central ions other than Fe, forming the inorganic metal-P framework in the MOF, may act as a more effective P-source in acid soils.

Characterization of Medicago truncatula reduced calcium oxalate crystal mutant alleles

USDA-ARS?s Scientific Manuscript database

Calcium oxalate crystal formation is common in plants. Formation of these crystals has been shown to function in plant defense, calcium regulation, and aluminum tolerance. Although calcium oxalate is common and plays important roles in plant development, our understanding of how these crystals form ...

Reduced active transcellular intestinal oxalate secretion contributes to the pathogenesis of obesity-associated hyperoxaluria.

PubMed

Amin, Ruhul; Asplin, John; Jung, Daniel; Bashir, Mohamed; Alshaikh, Altayeb; Ratakonda, Sireesha; Sharma, Sapna; Jeon, Sohee; Granja, Ignacio; Matern, Dietrich; Hassan, Hatim

2018-05-01

Most kidney stones are composed of calcium oxalate, and minor changes in urine oxalate affect the stone risk. Obesity is a risk factor for kidney stones and a positive correlation of unknown etiology between increased body size, and elevated urinary oxalate excretion has been reported. Here, we used obese ob/ob (ob) mice to elucidate the pathogenesis of obesity-associated hyperoxaluria. These ob mice have significant hyperoxaluria (3.3-fold) compared with control mice, which is not due to overeating as shown by pair-feeding studies. Dietary oxalate removal greatly ameliorated this hyperoxaluria, confirming that it is largely enteric in origin. Transporter SLC26A6 (A6) plays an essential role in active transcellular intestinal oxalate secretion, and ob mice have significantly reduced jejunal A6 mRNA (- 80%) and total protein (- 62%) expression. While net oxalate secretion was observed in control jejunal tissues mounted in Ussing chambers, net absorption was seen in ob tissues, due to significantly reduced secretion. We hypothesized that the obesity-associated increase in intestinal and systemic inflammation, as reflected by elevated proinflammatory cytokines, suppresses A6-mediated intestinal oxalate secretion and contributes to obesity-associated hyperoxaluria. Indeed, proinflammatory cytokines (elevated in ob mice) significantly decreased intestinal oxalate transport in vitro by reducing A6 mRNA and total protein expression. Proinflammatory cytokines also significantly reduced active mouse jejunal oxalate secretion, converting oxalate transport from net secretion in vehicle-treated tissues to net absorption in proinflammatory cytokines-treated tissues. Thus, reduced active intestinal oxalate secretion, likely secondary to local and systemic inflammation, contributes to the pathogenesis of obesity-associated hyperoxaluria. Hence, proinflammatory cytokines represent potential therapeutic targets. Copyright © 2017 International Society of Nephrology. Published by

Voltage Control of Rare-Earth Magnetic Moments at the Magnetic-Insulator-Metal Interface

NASA Astrophysics Data System (ADS)

Leon, Alejandro O.; Cahaya, Adam B.; Bauer, Gerrit E. W.

2018-01-01

The large spin-orbit interaction in the lanthanides implies a strong coupling between their internal charge and spin degrees of freedom. We formulate the coupling between the voltage and the local magnetic moments of rare-earth atoms with a partially filled 4 f shell at the interface between an insulator and a metal. The rare-earth-mediated torques allow the power-efficient control of spintronic devices by electric-field-induced ferromagnetic resonance and magnetization switching.

Effect of oxalate on the dissolution rates of oligoclase and tremolite

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

Mast, M.A.; Drever, J.I.

1987-09-01

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22/sup 0/C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of release ofmore » Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si. Large transient spikes of Al or Si are observed when oxalate is added to or removed from the system. The cause of the spikes is unknown; the authors suggest adsorption feldspar surfaces away from sites of active dissolution as a possibility. The rate of dissolution of tremolite is independent of pH over the pH range 2-5, and decreases at higher pH. The rate of dissolution of oligoclase in these experiments was independent of pH over the pH range 4-9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.« less

Facile self-assembly and stabilization of metal oxide nanoparticles.

PubMed

Charbonneau, Cecile; Holliman, Peter J; Davies, Matthew L; Watson, Trystan M; Worsley, David A

2015-03-15

This paper describes a facile method of self-assembling different metal oxide nanoparticles into nanostructured materials via di-carboxylate linkers (oxalic acid) using TiO2 as an example. In this method, the di-carboxylate linkers react with surface hydroxyls on metal oxide nanoparticles forming covalent, ester-like bonds, which enable the binding of two metal oxide particles, one at either end of the linker and facilitates efficient self-assembly of one group of metal oxide nanoparticles homogeneously distributed onto the surface of another group. The oxalate linkers can then be removed by thermal decomposition. This approach is shown to be effective using differently-sized TiO2 nanoparticles, namely in-house synthesized 3-5nm anatase nanocrystals and Degussa P25 titania particles (mean 21nm particle size). Our data show that the application of a high temperature heat treatment (450°C for 30min), conventionally applied to achieve a stable porous structure by thermal decomposition of the linker molecules and by inducing inter-particle necking, damages the surface area of the nanostructured material. However, here we show that sintering at 300°C for 30min or by flash near infrared radiation sintering for 12s efficiently decomposes the oxalate linkers and stabilizes the nanostructure of the material whilst maintaining its high surface area. Copyright © 2013 Elsevier Inc. All rights reserved.

Turning sunlight into stone: the oxalate-carbonate pathway in a tropical tree ecosystem

NASA Astrophysics Data System (ADS)

Cailleau, G.; Braissant, O.; Verrecchia, E. P.

2011-07-01

An African oxalogenic tree, the iroko tree (Milicia excelsa), has the property to enhance carbonate precipitation in tropical oxisols, where such accumulations are not expected due to the acidic conditions in these types of soils. This uncommon process is linked to the oxalate-carbonate pathway, which increases soil pH through oxalate oxidation. In order to investigate the oxalate-carbonate pathway in the iroko system, fluxes of matter have been identified, described, and evaluated from field to microscopic scales. In the first centimeters of the soil profile, decaying of the organic matter allows the release of whewellite crystals, mainly due to the action of termites and saprophytic fungi. In addition, a concomitant flux of carbonate formed in wood tissues contributes to the carbonate flux and is identified as a direct consequence of wood feeding by termites. Nevertheless, calcite biomineralization of the tree is not a consequence of in situ oxalate consumption, but rather related to the oxalate oxidation inside the upper part of the soil. The consequence of this oxidation is the presence of carbonate ions in the soil solution pumped through the roots, leading to preferential mineralization of the roots and the trunk base. An ideal scenario for the iroko biomineralization and soil carbonate accumulation starts with oxalatization: as the iroko tree grows, the organic matter flux to the soil constitutes the litter, and an oxalate pool is formed on the forest ground. Then, wood rotting agents (mainly termites, saprophytic fungi, and bacteria) release significant amounts of oxalate crystals from decaying plant tissues. In addition, some of these agents are themselves producers of oxalate (e.g. fungi). Both processes contribute to a soil pool of "available" oxalate crystals. Oxalate consumption by oxalotrophic bacteria can then start. Carbonate and calcium ions present in the soil solution represent the end products of the oxalate-carbonate pathway. The solution is

Turning sunlight into stone: the oxalate-carbonate pathway in a tropical tree ecosystem

NASA Astrophysics Data System (ADS)

Cailleau, G.; Braissant, O.; Verrecchia, E. P.

2011-02-01

An African oxalogenic tree, the iroko tree (Milicia excelsa), has the property to enhance carbonate precipitation in tropical oxisols, where such accumulations are not expected due to the theoretical acidic conditions of these soils. This uncommon process is linked to the oxalate-carbonate pathway, which increases soil pH through oxalate oxidation. In order to investigate the oxalate-carbonate pathway in the iroko system, fluxes of matter have been identified, described, and evaluated from field to microscopic scales. In the first centimeters of the soil profile, decaying of the organic matter allows the release of whewellite crystals, mainly due to the action of termites and saprophytic fungi. Regarding the carbonate flux, another direct consequence of wood feeding is a concomitant flux of carbonate formed in wood tissues, which is not consumed by termites. Nevertheless, calcite biomineralization of the tree is not a consequence of in situ oxalate consumption, but rather related to the oxalate oxidation inside the upper part of the soil. The consequence of this oxidation is the presence of carbonate ions in the soil solution pumped through the roots, leading to preferential mineralization of the roots and the trunk base. An ideal scenario for the iroko biomineralization and soil carbonate accumulation starts with oxalatization: as the iroko tree grows, the organic matter flux to the soil constitutes the litter. Therefore, an oxalate pool is formed on the forest ground. Then, wood rotting gents (mainly termites, fungi, and bacteria) release significant amounts of oxalate crystals from decaying plant tissues. In addition some of these gents are themselves producers of oxalate (fungi). Both processes contribute to a soil pool of "available" oxalate crystals. Oxalate consumption by oxalotrophic bacteria can start. Carbonate and calcium ions present in the soil solution represent the end products of the oxalate-carbonate pathway. The solution is pumped through the

Rare Earth Extraction from NdFeB Magnet Using a Closed-Loop Acid Process.

PubMed

Kitagawa, Jiro; Uemura, Ryohei

2017-08-14

There is considerable interest in extraction of rare earth elements from NdFeB magnets to enable recycling of these elements. In practical extraction methods using wet processes, the acid waste solution discharge is a problem that must be resolved to reduce the environmental impact of the process. Here, we present an encouraging demonstration of rare earth element extraction from a NdFeB magnet using a closed-loop hydrochloric acid (HCl)-based process. The extraction method is based on corrosion of the magnet in a pretreatment stage and a subsequent ionic liquid technique for Fe extraction from the HCl solution. The rare earth elements are then precipitated using oxalic acid. Triple extraction has been conducted and the recovery ratio of the rare earth elements from the solution is approximately 50% for each extraction process, as compared to almost 100% recovery when using a one-shot extraction process without the ionic liquid but with sufficient oxalic acid. Despite its reduced extraction efficiency, the proposed method with its small number of procedures at almost room temperature is still highly advantageous in terms of both cost and environmental friendliness. This study represents an initial step towards realization of a closed-loop acid process for recycling of rare earth elements.

Inorganic salts interact with oxalic acid in submicron particles to form material with low hygroscopicity and volatility

NASA Astrophysics Data System (ADS)

Drozd, G.; Woo, J.; Häkkinen, S. A. K.; Nenes, A.; McNeill, V. F.

2014-05-01

Volatility and hygroscopicity are two key properties of organic aerosol components, and both are strongly related to chemical identity. While the hygroscopicities of pure salts, di-carboxylic acids (DCA), and DCA salts are known, the hygroscopicity of internal mixtures of these components, as they are typically found in the atmosphere, has not been fully characterized. Here we show that inorganic-organic component interactions typically not considered in atmospheric models can lead to very strongly bound metal-organic complexes and greatly affect aerosol volatility and hygroscopicity; in particular, the bi-dentate binding of DCA to soluble inorganic ions. We have studied the volatility of pure, dry organic salt particles and the hygroscopicity of internal mixtures of oxalic acid (OxA, the dominant DCA in the atmosphere) and a number of salts, both mono- and di-valent. The formation of very low volatility organic salts was confirmed, with minimal evaporation of oxalate salt particles below 75 °C. Dramatic increases in the cloud condensation nuclei (CCN) activation diameter for particles with di-valent salts (e.g., CaCl2) and relatively small particle volume fractions of OxA indicate that standard volume additivity rules for hygroscopicity do not apply. Thus small organic compounds with high O : C ratios are capable of forming low-volatility and very low hygroscopicity particles. Given current knowledge of the formation mechanisms of OxA and M-Ox salts, surface enrichment of insoluble M-Ox salts is expected. The resulting formation of an insoluble coating of metal-oxalate salts can explain low-particle hygroscopicities. The formation of particles with a hard coating could offer an alternative explanation for observations of glass-like particles without the need for a phase transition.

Bifidobacterium animalis subsp. lactis decreases urinary oxalate excretion in a mouse model of primary hyperoxaluria

PubMed Central

Whittamore, Jonathan M.; Hatch, Marguerite

2015-01-01

Hyperoxaluria significantly increases the risk of calcium oxalate kidney stone formation. Since several bacteria have been shown to metabolize oxalate in vitro, including probiotic bifidobacteria, we focused on the efficiency and possible mechanisms by which bifidobacteria can infuence oxalate handling in vivo, especially in the intestines, and compared these results with the reported effects of Oxalobacter formigenes. Bifidobacterium animalis subsp. lactis DSM 10140 and B. adolescentis ATCC 15703 were administered to wild-type (WT) mice and to mice defcient in the hepatic enzyme alanine-glyoxylate aminotransferase (Agxt−/−, a mouse model of Primary Hyperoxaluria) that were fed an oxalate-supplemented diet. The administration of B. animalis subsp. lactis led to a significant decrease in urinary oxalate excretion in WT and Agxt−/− mice when compared to treatment with B. adolescent-is. Detection of B. animalis subsp. lactis in feces revealed that 3 weeks after oral gavage with the bacteria 64 % of WT mice, but only 37 % of Agxt−/− mice were colonized. Examining intestinal oxalate fuxes showed there were no significant changes to net oxalate secretion in colonized animals and were therefore not associated with the changes in urinary oxalate excretion. These results indicate that colonization with B. animalis subsp. lactis decreased urinary oxalate excretion by degrading dietary oxalate thus limiting its absorption across the intestine but it did not promote enteric oxalate excretion as reported for O. formigenes. Preventive or therapeutic administration of B. animalis subsp. lactis appears to have some potential to beneficially infuence dietary hyperoxaluria in mice. PMID:25269440

Effect of Oxalic Acid Treatment on Sediment Arsenic Concentrations and Lability under Reducing Conditions

PubMed Central

Sun, Jing; Bostick, Benjamin C.; Mailloux, Brian J.; Ross, James M.; Chillrud, Steven N.

2016-01-01

Oxalic acid enhances arsenic (As) mobilization by dissolving As host minerals and competing for sorption sites. Oxalic acid amendments thus could potentially improve the efficiency of widely used pump-and-treat (P&T) remediation. This study investigates the effectiveness of oxalic acid on As mobilization from contaminated sediments with different As input sources and redox conditions, and examines whether residual sediment As after oxalic acid treatment can still be reductively mobilized. Batch extraction, column, and microcosm experiments were performed in the laboratory using sediments from the Dover Municipal Landfill and the Vineland Chemical Company Superfund sites. Oxalic acid mobilized As from both Dover and Vineland sediments, although the efficiency rates were different. The residual As in both Dover and Vineland sediments after oxalic acid treatment was less vulnerable to microbial reduction than before the treatment. Oxalic acid could thus improve the efficiency of P&T. X-ray absorption spectroscopy analysis indicated that the Vineland sediment samples still contained reactive Fe(III) minerals after oxalic acid treatment, and thus released more As into solution under reducing conditions than the Dover samples. Therefore, the efficacy of P&T must consider sediment Fe mineralogy when evaluating its overall potential for remediating groundwater As. PMID:26970042

Successful treatment of sodium oxalate induced urolithiasis with Helichrysum flowers.

PubMed

Onaran, Metin; Orhan, Nilüfer; Farahvash, Amirali; Ekin, Hasya Nazlı; Kocabıyık, Murat; Gönül, İpek Işık; Şen, İlker; Aslan, Mustafa

2016-06-20

Helichrysum (Asteraceae) flowers, known as "altın otu, yayla çiçeği, kudama çiçeği" , are widely used to remove kidney stones and for their diuretic properties in Turkey. To determine the curative effect of infusions prepared from capitulums of Helichrysum graveolens (M. Bieb.) Sweet (HG) and H. stoechas ssp. barellieri (Ten.) Nyman (HS) on sodium oxalate induced kidney stones. Infusions prepared from the capitulums of HG and HS were tested for their curative effect on calcium oxalate deposition induced by sodium oxalate (70mg/kg i.p.). Following the injection of sodium oxalate for 5 days, plant extracts were administered to rats at two different doses. Potassium citrate was used as positive control. Water intake, urine volume, body, liver and kidney weights were measured; biochemical and hematological analyses were conducted on urine and blood samples. Additionally, histopathological examinations were done on kidney samples. H. stoechas extract showed prominent effect at 156mg/kg dose (stone formation score: 0.33), whereas number of kidney stones was maximum in sodium oxalate group (stone formation score: 2.33). The reduction in the uric acid and oxalate levels of urine samples and the elevation in the urine citrate levels are significant and promising in extract groups. Some hematological, biochemical and enzymatic markers are also ameliorated by the extracts. This is the first report on the curative effect of immortal flowers. Our preliminary study indicated that Helichrysum extracts may be used for treatment of urolithiasis and Helichrysum extracts are an alternative therapy to potassium citrate for patients suffering from kidney stones. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Two sodium and lanthanide(III) MOFs based on oxalate and V-shaped 4,4‧-oxybis(benzoate) ligands: Hydrothermal synthesis, crystal structure, and luminescence properties

NASA Astrophysics Data System (ADS)

Wang, Chongchen; Guo, Guangliang; Wang, Peng

2013-01-01

Two lanthanide based metal-organic frameworks, [NaLn(oba)(ox)(H2O)] (Lndbnd6 Eu(1) and Sm(2)) were obtained from 4,4'-oxybisbenzoic acid, sodium oxalate and corresponding lanthanide salts by hydrothermal synthesis. They were characterized by single-crystal X-ray diffraction, IR spectra, and photoluminescent spectra. The crystallographic data reveals that complexes 1 and 2 are isomorphous and isostructural, composed of three-dimensional framework built up of distorted tricapped trigonal EuO9 units, distorted octahedron NaO6 units, 4,4'-oxybis(benzoate) and oxalate. The carboxylate oxygen atoms of the 4,4'-oxybis(benzoate) and oxalate ligand are coordinated to lanthanide ions and sodium ions, resulting into two-dimensional inorganic sheets, which are further linked into three-dimensional network by organic ligands. Thermogravimetric analyses of 1-2 display a considerable thermal stability. Photoluminescent measurements indicated that europium complex 1 displayed strong red emission.

Efficacy of Mixtures of Magnesium, Citrate and Phytate as Calcium Oxalate Crystallization Inhibitors in Urine.

PubMed

Grases, Felix; Rodriguez, Adrian; Costa-Bauza, Antonia

2015-09-01

The main aim of the current study was to evaluate the effectiveness of mixtures of magnesium, citrate and phytate as calcium oxalate crystallization inhibitors. A turbidimetric assay in synthetic urine was performed to obtain induction times for calcium oxalate crystallization in the absence and presence of different mixtures of inhibitors. The morphology of calcium oxalate crystals in the absence or presence of inhibitors and mixtures of the inhibitors was evaluated in 2 crystallization experiments at low and high calcium oxalate supersaturation. The crystals formed were examined using scanning electron microscopy. Examination of crystallization induction times revealed clear inhibitory effects of magnesium, citrate and phytate on calcium oxalate crystallization, supporting usefulness in the treatment and prevention of calcium oxalate nephrolithiasis. Significant synergistic effects between magnesium and phytate were observed. Scanning electron microscopy images revealed that phytate is a powerful crystal growth inhibitor of calcium oxalate, totally preventing the formation of trihydrate and monohydrate. In addition to crystallization inhibition capacity, citrate and magnesium avoided calcium oxalate crystallization by decreasing its supersaturation. The synergistic effect between magnesium and phytate on calcium oxalate crystallization suggests that a combination of these 2 compounds may be highly useful as antilithiasis therapy. Copyright © 2015 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Adsorption of alkali and alkaline earth metal atoms and dimers on monolayer germanium carbide

NASA Astrophysics Data System (ADS)

Gökçe, Aytaç Gürhan; Ersan, Fatih

2017-01-01

First-principles plane wave calculations have been performed to study the adsorption of alkali and alkaline earth metals on monolayer germanium carbide (GeC). We found that the favourable adsorption sites on GeC sheet for single alkali and alkaline earth adatoms are generally different from graphene or germanene. Among them, Mg, Na and their dimers have weakly bounded to GeC due to their closed valence electron shells, so they may have high mobility on GeC. Two different levels of adatom coverage (? and ?) have been investigated and we concluded that different electronic structures and magnetic moments for both coverages owing to alkali and alkaline earth atoms have long range electrostatic interactions. Lithium atom prefers to adsorbed on hollow site similar to other group-IV monolayers and the adsorption results in metallisation of GeC instead of semiconducting behaviour. Na and K adsorption can induce 1 ? total magnetic moment on GeC structures and they have shown semiconductor property which may have potential use in spintronic devices. We also showed that alkali or alkaline earth metal atoms can form dimer on GeC sheet. Calculated adsorption energies suggest that clustering of alkali and alkaline earth atoms is energetically favourable. All dimer adsorbed GeC systems have nonmagnetic semiconductor property with varying band gaps from 0.391 to 1.311 eV which are very suitable values for various device applications.

Acute oxalate nephropathy due to 'Averrhoa bilimbi' fruit juice ingestion.

PubMed

Bakul, G; Unni, V N; Seethaleksmy, N V; Mathew, A; Rajesh, R; Kurien, G; Rajesh, J; Jayaraj, P M; Kishore, D S; Jose, P P

2013-07-01

Irumban puli (Averrhoa bilimbi) is commonly used as a traditional remedy in the state of Kerala. Freshly made concentrated juice has a very high oxalic acid content and consumption carries a high risk of developing acute renal failure (ARF) by deposition of calcium oxalate crystals in renal tubules. Acute oxalate nephropathy (AON) due to secondary oxalosis after consumption of Irumban puli juice is uncommon. AON due to A. bilimbi has not been reported before. We present a series of ten patients from five hospitals in the State of Kerala who developed ARF after intake of I. puli fruit juice. Seven patients needed hemodialysis whereas the other three improved with conservative management.

Enhanced Nitrogen Availability in Karst Ecosystems by Oxalic Acid Release in the Rhizosphere

PubMed Central

Pan, Fujing; Liang, Yueming; Zhang, Wei; Zhao, Jie; Wang, Kelin

2016-01-01

In karst ecosystems, a high level of CaCO3 enhances the stabilization of soil organic matter (SOM) and causes nitrogen (N) and/or phosphorus (P) limitation in plants. Oxalic acid has been suggested to be involved in the nutrient-acquisition strategy of plants because its addition can temporarily relieve nutrient limitation. Therefore, understanding how oxalic acid drives N availability may help support successful vegetation restoration in the karst ecosystems of southwest China. We tested a model suggested by Clarholm et al. (2015) where oxalate reacts with Ca bridges in SOM, thus exposing previously protected areas to enzymatic attacks in a way that releases N for local uptake. We studied the effects of oxalic acid, microbial biomass carbon (MBC), and β-1,4-N-acetylglucosaminidase (NAG) on potential N mineralization rates in rhizosphere soils of four plant species (two shrubs and two trees) in karst areas. The results showed that rhizosphere soils of shrubs grown on formerly deforested land had significantly lower oxalic acid concentrations and NAG activity than that of trees in a 200-year-old forest. The levels of MBC in rhizosphere soils of shrubs were significantly lower than those of trees in the growing season, but the measure of shrubs and trees were similar in the non-growing season; the potential N mineralization rates showed a reverse pattern. Positive relationships were found among oxalic acid, MBC, NAG activity, and potential N mineralization rates for both shrubs and trees. This indicated that oxalic acid, microbes, and NAG may enhance N availability for acquisition by plants. Path analysis showed that oxalic acid enhanced potential N mineralization rates indirectly through inducing microbes and NAG activities. We found that the exudation of oxalic acid clearly provides an important mechanism that allows plants to enhance nutrient acquisition in karst ecosystems. PMID:27252713

Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique

PubMed Central

Nigl, Thomas P.; Smith, Nathan D.; Lichtenstein, Timothy; Gesualdi, Jarrod; Kumar, Kuldeep; Kim, Hojong

2017-01-01

A novel electrochemical cell based on a CaF2 solid-state electrolyte has been developed to measure the electromotive force (emf) of binary alkaline earth-liquid metal alloys as functions of both composition and temperature in order to acquire thermodynamic data. The cell consists of a chemically stable solid-state CaF2-AF2 electrolyte (where A is the alkaline-earth element such as Ca, Sr, or Ba), with binary A-B alloy (where B is the liquid metal such as Bi or Sb) working electrodes, and a pure A metal reference electrode. Emf data are collected over a temperature range of 723 K to 1,123 K in 25 K increments for multiple alloy compositions per experiment and the results are analyzed to yield activity values, phase transition temperatures, and partial molar entropies/enthalpies for each composition. PMID:29155770

Differential Effects of Low-Molecular-Weight Organic Acids on the Mobilization of Soil-Borne Arsenic and Trace Metals.

PubMed

Nworie, Obinna Elijah; Qin, Junhao; Lin, Chuxia

2017-08-21

A batch experiment was conducted to examine the effects of six low-molecular-weight organic acids on the mobilization of arsenic and trace metals from a range of contaminated soils. The results showed that the organic acids behaved differently when reacting with soil-borne As and trace metals. Oxalic acid and acetic acid had the strongest and weakest capacity to mobilize the investigated elements, respectively. The solubilisation of iron oxides by the organic acids appears to play a critical role in mobilizing other trace metals and As. Apart from acidification and complexation, reductive dissolution played a dominant role in the dissolution of iron oxides in the presence of oxalic acid, while acidification tended to be more important for dissolving iron oxides in the presence of other organic acids. The unique capacity of oxalic acid to solubilize iron oxides tended to affect the mobilization of other elements in different ways. For Cu, Mn, and Zn, acidification-driven mobilization was likely to be dominant while complexation might play a major role in Pb mobilization. The formation of soluble Fe and Pb oxalate complexes could effectively prevent arsenate or arsenite from combining with these metals to form solid phases of Fe or Pb arsenate or arsenite.

Recovery of rare earths from spent NdFeB magnets of wind turbine: Leaching and kinetic aspects.

PubMed

Kumari, Aarti; Sinha, Manish Kumar; Pramanik, Swati; Sahu, Sushanta Kumar

2018-05-01

Increasing demands of rare earth (RE) metals for advanced technological applications coupled with the scarcity of primary resources have led to the development of processes to treat secondary resources like scraps or end of life products that are often rich in such metals. Spent NdFeB magnet may serve as a potential source of rare earths containing around ∼30% of neodymium and other rare earths. In the present investigation, a pyro-hydrometallurgical process has been developed to recover rare earth elements (Nd, Pr and Dy) from the spent wind turbine magnet. The spent magnet is demagnetized and roasted at 1123 K to convert rare earths and iron to their respective oxides. Roasting of the magnet not only provides selectivity, but enhances the leaching efficiency also. The leaching of the roasted sample with 0.5 M hydrochloric acid at 368 K, 100 g/L pulp density and 500 rpm for 300 min selectively recovers the rare earth elements almost quantitatively leaving iron oxide in the residue. Leaching of rare earth elements with hydrochloric acid follows the mixed controlled kinetic model with activation energy (E a ) of 30.1 kJ/mol in the temperature range 348-368 K. The leaching mechanism is further established by characterizing the leach residues obtained at different time intervals by scanning electron microscopy- energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Individual rare earth elements from the leach solution containing 16.8 g/L of Nd, 3.8 g/L Pr, 0.28 g/L of Dy and other minor impurity elements could be separated by solvent extraction. However, mixed rare earth oxide of 99% purity was produced by oxalate precipitation followed by roasting. The leach residue comprising of pure hematite has a potential to be used as pigment or can find other applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Arthritis associated with calcium oxalate crystals in an anephric patient treated with peritoneal dialysis

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

Rosenthal, A.; Ryan, L.M.; McCarty, D.J.

1988-09-02

The authors report a case of calcium oxalate arthropathy in a woman undergoing intermittent peritoneal dialysis who was not receiving pharmacologic doses of ascorbic acid. She developed acute arthritis, with calcium oxalate crystals in Heberden's and Bouchard's nodes, a phenomenon previously described in gout. Intermittent peritoneal dialysis may be less efficient than hemodialysis in clearing oxalate, and physicians should now consider calcium oxalate-associated arthritis in patients undergoing peritoneal dialysis who are not receiving large doses of ascorbic acid.

Ground-state properties of rare-earth metals: an evaluation of density-functional theory.

PubMed

Söderlind, Per; Turchi, P E A; Landa, A; Lordi, V

2014-10-15

The rare-earth metals have important technological applications due to their magnetic properties, but are scarce and expensive. Development of high-performance magnetic materials with less rare-earth content is desired, but theoretical modeling is hampered by complexities of the rare earths electronic structure. The existence of correlated (atomic-like) 4f electrons in the vicinity of the valence band makes any first-principles theory challenging. Here, we apply and evaluate the efficacy of density-functional theory for the series of lanthanides (rare earths), investigating the influence of the electron exchange and correlation functional, spin-orbit interaction, and orbital polarization. As a reference, the results are compared with those of the so-called 'standard model' of the lanthanides in which electrons are constrained to occupy 4f core states with no hybridization with the valence electrons. Some comparisons are also made with models designed for strong electron correlations. Our results suggest that spin-orbit coupling and orbital polarization are important, particularly for the magnitude of the magnetic moments, and that calculated equilibrium volumes, bulk moduli, and magnetic moments show correct trends overall. However, the precision of the calculated properties is not at the level of that found for simpler metals in the Periodic Table of Elements, and the electronic structures do not accurately reproduce x-ray photoemission spectra.

The Electronic Structure and Optical Properties of Anatase TiO₂ with Rare Earth Metal Dopants from First-Principles Calculations.

PubMed

Xie, Kefeng; Jia, Qiangqiang; Wang, Yizhe; Zhang, Wenxue; Xu, Jingcheng

2018-01-24

The electronic and optical properties of the rare earth metal atom-doped anatase TiO₂ have been investigated systematically via density functional theory calculations. The results show that TiO₂ doped by Ce or Pr is the optimal choice because of its small band gap and strong optical absorption. Rare earth metal atom doping induces several impurity states that tune the location of valence and conduction bands and an obvious lattice distortion that should reduce the probability of electron-hole recombination. This effect of band change originates from the 4 f electrons of the rare earth metal atoms, which leads to an improved visible light absorption. This finding indicates that the electronic structure of anatase TiO₂ is tuned by the introduction of impurity atoms.

Prophylactic role of phycocyanin: a study of oxalate mediated renal cell injury.

PubMed

Farooq, Shukkur Muhammed; Asokan, Devarajan; Kalaiselvi, Periandavan; Sakthivel, Ramasamy; Varalakshmi, Palaninathan

2004-08-10

Oxalate induced renal calculi formation and the associated renal injury is thought to be caused by free radical mediated mechanisms. An in vivo model was used to investigate the effect of phycocyanin (from Spirulina platensis), a known antioxidant, against calcium oxalate urolithiasis. Male Wistar rats were divided into four groups. Hyperoxaluria was induced in two of these groups by intraperitoneal infusion of sodium oxalate (70 mg/kg) and a pretreatment of phycocyanin (100 mg/kg) as a single oral dosage was given, 1h prior to sodium oxalate infusion. An untreated control and drug control (phycocyanin alone) were also included in the study. We observed that phycocyanin significantly controlled the early biochemical changes in calcium oxalate stone formation. The antiurolithic nature of the drug was evaluated by the assessment of urinary risk factors and light microscopic observation of urinary crystals. Renal tubular damage as divulged by urinary marker enzymes (alkaline phosphatase, acid phosphatase and gamma-glutamyl transferase) and histopathological observations such as decreased tubulointerstitial, tubular dilatation and mononuclear inflammatory cells, indicated that renal damage was minimised in drug-pretreated group. Oxalate levels (P < 0.001) and lipid peroxidation (P < 0.001) in kidney tissue were significantly controlled by drug pretreatment, suggesting the ability of phycocyanin to quench the free radicals, thereby preventing the lipid peroxidation mediated tissue damage and oxalate entry. This accounts for the prevention of CaOx stones. Thus, the present analysis revealed the antioxidant and antiurolithic potential of phycocyanin thereby projecting it as a promising therapeutic agent against renal cell injury associated kidney stone formation.

Thermodynamic Investigation of the Reduction-Distillation Process for Rare Earth Metals Production

NASA Astrophysics Data System (ADS)

Judge, W. D.; Azimi, G.

2017-10-01

Owing to their high vapor pressure, the four rare earth metals samarium, europium, thulium, and ytterbium are produced by reduction-distillation whereby their oxides are reduced with metallic lanthanum in vacuo, and the produced metal is subsequently vaporized off. Here, we performed a thorough thermodynamic investigation to establish a fundamental understanding of the reduction-distillation process. Thermodynamic functions including vapor pressures, Gibbs free energies, and enthalpies of reaction were calculated and compared with available experimental data. Furthermore, the kinetics of the process was explored and theoretical evaporation rates were calculated from thermodynamic data. The thermodynamic model developed in this work can help optimize processing conditions to maximize the yield and improve the overall process.

Distribution behavior of uranium, neptunium, rare-earth elements ( Y, La, Ce, Nd, Sm, Eu, Gd) and alkaline-earth metals (Sr,Ba) between molten LiClKCI eutectic salt and liquid cadmium or bismuth

NASA Astrophysics Data System (ADS)

Kurata, M.; Sakamura, Y.; Hijikata, T.; Kinoshita, K.

1995-12-01

Distribution coefficients of uranium neptunium, eight rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) and two alkaline-earth metals (Sr and Ba) between molten LiCl-KCI eutectic salt and either liquid cadmium or bismuth were measured at 773 K. Separation factors of trivalent rare-earth elements to uranium or neptunium in the LiCl-KCl/Bi system were by one or two orders of magnitude larger than those in the LiCl-KCl/Cd system. On the contrary, the separation factors of alkaline-earth metals and divalent rare-earth elements to trivalent rare-earth elements were by one or two orders of magnitude smaller in the LiCl-KCl/Bi system.

Specific Inhibition of Hepatic Lactate Dehydrogenase Reduces Oxalate Production in Mouse Models of Primary Hyperoxaluria.

PubMed

Lai, Chengjung; Pursell, Natalie; Gierut, Jessica; Saxena, Utsav; Zhou, Wei; Dills, Michael; Diwanji, Rohan; Dutta, Chaitali; Koser, Martin; Nazef, Naim; Storr, Rachel; Kim, Boyoung; Martin-Higueras, Cristina; Salido, Eduardo; Wang, Weimin; Abrams, Marc; Dudek, Henryk; Brown, Bob D

2018-06-15

Primary hyperoxalurias (PHs) are autosomal recessive disorders caused by the overproduction of oxalate leading to calcium oxalate precipitation in the kidney and eventually to end-stage renal disease. One promising strategy to treat PHs is to reduce the hepatic production of oxalate through substrate reduction therapy by inhibiting liver-specific glycolate oxidase (GO), which controls the conversion of glycolate to glyoxylate, the proposed main precursor to oxalate. Alternatively, diminishing the amount of hepatic lactate dehydrogenase (LDH) expression, the proposed key enzyme responsible for converting glyoxylate to oxalate, should directly prevent the accumulation of oxalate in PH patients. Using RNAi, we provide the first in vivo evidence in mammals to support LDH as the key enzyme responsible for converting glyoxylate to oxalate. In addition, we demonstrate that reduction of hepatic LDH achieves efficient oxalate reduction and prevents calcium oxalate crystal deposition in genetically engineered mouse models of PH types 1 (PH1) and 2 (PH2), as well as in chemically induced PH mouse models. Repression of hepatic LDH in mice did not cause any acute elevation of circulating liver enzymes, lactate acidosis, or exertional myopathy, suggesting further evaluation of liver-specific inhibition of LDH as a potential approach for treating PH1 and PH2 is warranted. Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.

New technology of extracting the amount of rare earth metals from the red mud

NASA Astrophysics Data System (ADS)

Martoyan, G. A.; Karamyan, G. G.; Vardan, G. A.

2016-01-01

The paper outlined the environmental and economic problems associated with red mud - the waste generated in processing of bauxite ore for aluminum production. The chemical analysis of red mud has identified a number of useful elements including rare earth metals. The electromembrane technology of red mud processing with extraction of valuable elements is described. A possible scheme of separation of these metals through electrolysis is also given.

Coulometric Study of Rates of Oxalic Acid Adsorption at a Polycrystalline Platinum Electrode

DTIC Science & Technology

2012-09-01

Coulometric Study of Rates of Oxalic Acid Adsorption at a Polycrystalline Platinum Electrode by Sol Gilman ARL-TR-6165 September 2012...6165 September 2012 Coulometric Study of Rates of Oxalic Acid Adsorption at a Polycrystalline Platinum Electrode Sol Gilman Sensors and...3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE Coulometric Study of Rates of Oxalic Acid Adsorption at a Polycrystalline Platinum Electrode

Enzymatic oxalic acid regulation correlated with wood degradation in four brown-rot fungi

Treesearch

Anne Christine Steenkjær Hastrup; Frederick Green III; Patricia K. Lebow; Bo Jensen

2012-01-01

Oxalic acid is a key component in the initiation of brown-rot decay and it has been suggested that it plays multiple roles during the degradation process. Oxalic acid is accumulated to varying degrees among brown-rot fungi; however, details on active regulation are scarce. The accumulation of oxalic acid was measured in this study from wood degraded by the four brown-...

(Di­methyl­phosphor­yl)methanaminium hydrogen oxalate–oxalic acid (2/1)

PubMed Central

Bialek, Sebastian; Clemens, Rebecca; Reiss, Guido J.

2014-01-01

The reaction of (di­methyl­phosphor­yl)methanamine (dpma) with oxalic acid in ethanol yielded the title solvated salt, C3H11NOP+·C2HO4 −·0.5C2H2O4. Its asymmetric unit consists of one dpmaH+ cation, one hydrogen oxalate anion and a half-mol­ecule of oxalic acid located around a twofold rotation axis. The H atom of the hydrogen oxalate anion is statistically disordered over two positions that are trans to each other. The hydrogen oxalate monoanion is not planar (bend angle ∼16°) whereas the oxalic acid molecule shows a significantly smaller bend angle (∼7°). In the crystal, the components are connected by strong O—H⋯O and much weaker N—H⋯O hydrogen bonds, leading to the formation of layers extending parallel to (001). The structure was refined from a racemically twinned crystal with twin components in an approximate 1:1 ratio. PMID:24765013

Characterization of calcium oxalate defective (cod) 3 mutant from Medicago truncatula

USDA-ARS?s Scientific Manuscript database

Many plants invest a considerable amount of resources and energy into the formation of calcium oxalate crystals. Assigned roles for plant crystal formation include functions in defense, calcium regulation, and aluminum tolerance. From a human health standpoint, oxalate present in edible plant tiss...

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Neutron Diffraction Studies of Some Rare Earth-Transition Metal Deuterides.

DTIC Science & Technology

1986-05-01

RD-A168 M NEUTRON DIFFRACTION STUDIES OF SONE RARE EARTH-TRANSITION METAL DEUTERIDES(U) MISSOURI UNIV-ROLLR MATERIALS RESEARCH CENTER N J JAMES MY 86...REPORT William J. James OTtO -il May 1986 ZLECTEJU U. S. Army Research Office DAAG29-83-K-01 59 ".;’ Graduate Center for Materials Research ...9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT, PROJECT. TASK AREA & WORK UNIT NUMBERS 2* Graduate Center for Materials Research

Interaction of Gas Phase Oxalic Acid with Ammonia and its Atmospheric Implications

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

Peng, Xiu-Qiu; Liu, Yi-Rong; Huang, Teng

Oxalic acid is believed to play an important role in the formation and growth of atmospheric organic aerosols. However, as a common organic acid, the understanding of the larger clusters formed by gas phase oxalic acid with multiple ammonia molecules is incomplete. In this work, the structural characteristics and thermodynamics of oxalic acid clusters with up to six ammonia molecules have been investigated at the PW91PW91/6-311++G(3df,3pd) level of theory. We found that oxalic acid forms relatively stable clusters with ammonia molecules, and that ionization events play a key role. The analyses of the thermodynamics and atmospheric relevance indicate that themore » heterodimer (H2C2O4)(NH3) shows an obvious relative concentration in the atmosphere, and thus likely participates in new particle formation. However, with increasing number of ammonia molecules, the concentration of clusters decreases gradually. Additionally, clusters of oxalic acid with ammonia molecules are predicted to form favorably in low temperature conditions and show high Rayleigh scattering intensities.« less

In-cloud oxalate formation in the global troposphere: a 3-D modeling study

NASA Astrophysics Data System (ADS)

Myriokefalitakis, S.; Tsigaridis, K.; Mihalopoulos, N.; Sciare, J.; Nenes, A.; Segers, A.; Kanakidou, M.

2011-01-01

Organic acids attract increasing attention as contributors to atmospheric acidity, secondary organic aerosol mass and aerosol hygroscopicity. Oxalic acid is globally the most abundant dicarboxylic acid, formed via chemical oxidation of gas-phase precursors in the aqueous phase of aerosols and droplets. Its lifecycle and atmospheric global distribution remain highly uncertain and are the focus of this study. The first global spatial and temporal distribution of oxalate, simulated using a state-of-the-art aqueous phase chemical scheme embedded within the global 3-dimensional chemistry/transport model TM4-ECPL, is here presented. The model accounts for comprehensive gas-phase chemistry and its coupling with major aerosol constituents (including secondary organic aerosol). Model results are consistent with ambient observations of oxalate at rural and remote locations (slope = 0.83 ± 0.06, r2 = 0.67, N = 106) and suggest that aqueous phase chemistry contributes significantly to the global atmospheric burden of secondary organic aerosol. In TM4-ECPL most oxalate is formed in-clouds and less than 10% is produced in aerosol water. About 61% of the oxalate is removed via wet deposition, 35% by in-cloud reaction with hydroxyl radical and 4% by dry deposition. The global oxalate net chemical production is calculated to be about 17-27 Tg yr-1 with almost 91% originating from biogenic hydrocarbons, mainly isoprene. This condensed phase net source of oxalate in conjunction with a global mean turnover time against deposition of about 5 days, maintain oxalate's global tropospheric burden of 0.24-0.39 Tg that is about 13-19% of calculated total organic aerosol burden.

Effect of cinnamon and turmeric on urinary oxalate excretion, plasma lipids, and plasma glucose in healthy subjects.

PubMed

Tang, Minghua; Larson-Meyer, D Enette; Liebman, Michael

2008-05-01

High oxalate intake resulting from consuming supplemental doses of cinnamon and turmeric may increase risk of hyperoxaluria, a significant risk factor for urolithiasis. This study assessed urinary oxalate excretion from supplemental doses of cinnamon and turmeric as well as changes in fasting plasma glucose, cholesterol, and triacylglycerol concentrations. Eleven healthy subjects, aged 21-38 y, participated in an 8-wk, randomly assigned, crossover study that involved the ingestion of supplemental doses of cinnamon and turmeric for 4-wk periods that provided 55 mg oxalate/d. Oxalate load tests, which entailed the ingestion of a 63-mg dose of oxalate from the test spices, were performed after each 4-wk experimental period and at the study onset with water only (control treatment). Fasting plasma glucose and lipid concentrations were also assessed at these time points. Compared with the cinnamon and control treatments, turmeric ingestion led to a significantly higher urinary oxalate excretion during the oxalate load tests. There were no significant changes in fasting plasma glucose or lipids in conjunction with the 4-wk periods of either cinnamon or turmeric supplementation. The percentage of oxalate that was water soluble differed markedly between cinnamon (6%) and turmeric (91%), which appeared to be the primary cause of the greater urinary oxalate excretion/oxalate absorption from turmeric. The consumption of supplemental doses of turmeric, but not cinnamon, can significantly increase urinary oxalate levels, thereby increasing risk of kidney stone formation in susceptible individuals.

Oxalate content of different drinkable dilutions of tea infusions after different brewing times.

PubMed

Lotfi Yagin, Neda; Mahdavi, Reza; Nikniaz, Zeinab

2012-01-01

The aims of this study were to determine the effect of different brewing times and diluting on oxalate content of loose-packed black teas consumed in Tabriz, Iran. The oxalate content of black teas after brewing for 5, 10, 15, 30, 60 minutes was measured in triplicate by enzymatic assay. In order to attain the most acceptable dilution of tea infusions, tea samples which were brewed for 15, 30 and 60 minutes were diluted two (120 ml), three (80 ml) and four (60 ml) times respectively. There was a stepwise increase in oxalate concentrations associated with increased brewing times (P< 0.001) with oxalate contents ranging from 4.4 mg/240 ml for the 5 min to 6.3 mg/240 ml for 60 min brewing times, respectively. There were significant differences between the mean oxalate content of different dilutions after brewing for 15, 30 and 60 minutes (P< 0.001). The oxalate content of Iranian consumed black tea after different brewing times and different dilution was below the recommended levels. Therefore, it seems that consumption of black tea several times per day would not pose significant health risk in kidney stone patients and susceptible individuals.

Influence of oxalic acid on the dissolution kinetics of manganese oxide

NASA Astrophysics Data System (ADS)

Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

2012-11-01

The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

Vitamin C with metabolites: additional analysis suggests favorable changes in oxalate.

PubMed

Moyad, Mark A; Combs, Maile A; Baisley, Joshua E; Evans, Malkanthi

2009-01-01

A previously published randomized trial found a significant difference in the proportion of individuals experiencing oxalate reduction with a vitamin C with metabolites product compared with ascorbic acid (vitamin C). This represented a notable finding, which argued against the possibility of a chance finding due to the design and consistency of results. However, these researchers believed it was necessary to further analyze this study to continue to garner more insight on the strength or weakness of original findings. All favorable, neutral, and non-favorable changes of 24-hour oxalate from the previous clinical trial were grouped. Oxalate was considered to "decrease" or "increase" with each intervention only if a 10% or larger change occurred in the 24-hour oxalate baseline value when taking one product compared to another. A greater proportion of subjects taking both products at different time periods experienced favorable oxalate changes with vitamin C with metabolites product compared to ascorbic acid. If this reflects the true clinical scenario, this would represent an important clinical finding on a population level because at least 20% more individuals would experience a more favorable change. Regardless, this further analysis continues to suggest that the original observations were valid and could have positive clinical implications for some patients.

Extracellular nucleotides inhibit oxalate transport by human intestinal Caco-2-BBe cells through PKC-δ activation

PubMed Central

Amin, Ruhul; Sharma, Sapna; Ratakonda, Sireesha

2013-01-01

Nephrolithiasis remains a major health problem in Western countries. Seventy to 80% of kidney stones are composed of calcium oxalate, and small changes in urinary oxalate affect risk of kidney stone formation. Intestinal oxalate secretion mediated by the anion exchanger SLC26A6 plays an essential role in preventing hyperoxaluria and calcium oxalate nephrolithiasis, indicating that understanding the mechanisms regulating intestinal oxalate transport is critical for management of hyperoxaluria. Purinergic signaling modulates several intestinal processes through pathways including PKC activation, which we previously found to inhibit Slc26a6 activity in mouse duodenal tissue. We therefore examined whether purinergic stimulation with ATP and UTP affects oxalate transport by human intestinal Caco-2-BBe (C2) cells. We measured [14C]oxalate uptake in the presence of an outward Cl− gradient as an assay of Cl−/oxalate exchange activity, ≥50% of which is mediated by SLC26A6. We found that ATP and UTP significantly inhibited oxalate transport by C2 cells, an effect blocked by the PKC inhibitor Gö-6983. Utilizing pharmacological agonists and antagonists, as well as PKC-δ knockdown studies, we observed that ATP inhibits oxalate transport through the P2Y2 receptor, PLC, and PKC-δ. Biotinylation studies showed that ATP inhibits oxalate transport by lowering SLC26A6 surface expression. These findings are of potential relevance to pathophysiology of inflammatory bowel disease-associated hyperoxaluria, where supraphysiological levels of ATP/UTP are expected and overexpression of the P2Y2 receptor has been reported. We conclude that ATP and UTP inhibit oxalate transport by lowering SLC26A6 surface expression in C2 cells through signaling pathways including the P2Y2 purinergic receptor, PLC, and PKC-δ. PMID:23596171

Characterization of metal binding sites onto biochar using rare earth elements as a fingerprint.

PubMed

Pourret, Olivier; Houben, David

2018-02-01

The ability of biochar to immobilize metals relies on the amount of functional groups at its surface but the contribution of each functional groups (e.g. carboxylic, phenolic) to metal bonding is poorly known. Using a new approach based on previous works on rare earth element (REE) interactions with humic substances, we aim at elucidating the relative contribution of these binding sites to metal sorption under various conditions (i.e. pH and ionic strengths, IS). Using batch experiments, REE sorption onto biochar was analyzed from pH 3 to 9 and IS 10 -1 mol/L to 10 -3 mol/L. Rare earth element patterns show a Middle REE (MREE) downward concavity at acidic pH and low ionic strength. These patterns are in good agreement with existing datasets quantifying REE binding with humic substances. Indeed, the MREE downward concavity displayed by REE-biochar complexation pattern compares well with REE patterns with various organic compounds. This similarity in the REE complexation pattern shapes suggests that carboxylic groups are the main binding sites of REE in biochar. Overall, our results indicate that the strength of the metal bonding with biochar increases when pH and IS increase, suggesting that biochar is more efficient for long-term metal immobilization at near neutral pH and high ionic strength.

Novel Applications for Oxalate-Phosphate-Amine Metal-Organic-Frameworks (OPA-MOFs): Can an Iron-Based OPA-MOF Be Used as Slow-Release Fertilizer?

PubMed Central

Anstoetz, Manuela; Rose, Terry J.; Clark, Malcolm W.; Yee, Lachlan H.; Raymond, Carolyn A.; Vancov, Tony

2015-01-01

A porous iron-based oxalate-phosphate-amine metal-organic framework material (OPA-MOF) was investigated as a microbially-induced slow-release nitrogen (N) and phosphorus (P) fertilizer. Seedling growth, grain yields, nutrient uptake of wheat plants, and soil dynamics in incubated soil, were investigated using OPA-MOF vs standard P (triple-superphosphate) and N (urea) fertilizers in an acidic Ferralsol at two application rates (equivalent 120 and 40 kg N ha-1). While urea hydrolysis in the OPA-MOF treatment was rapid, conversion of ammonium to nitrate was significantly inhibited compared to urea treatment. Reduced wheat growth in OPA-MOF treatments was not caused by N-deficiency, but by limited P-bioavailability. Two likely reasons were slow P-mobilisation from the OPA-MOF or rapid P-binding in the acid soil. P-uptake and yield in OPA-MOF treatments were significantly higher than in nil-P controls, but significantly lower than in conventionally-fertilised plants. OPA-MOF showed potential as enhanced efficiency N fertilizer. However, as P-bioavailability was insufficient to meet plant demands, further work should determine if P-availability may be enhanced in alkaline soils, or whether central ions other than Fe, forming the inorganic metal-P framework in the MOF, may act as a more effective P-source in acid soils. PMID:26633174

Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

PubMed

Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

2016-02-01

The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge. Copyright © 2015 Elsevier Ltd. All rights reserved.

Atmospheric behaviour of particulate oxalate at UK urban background and rural sites

NASA Astrophysics Data System (ADS)

Laongsri, Bunthoon; Harrison, Roy M.

2013-06-01

Oxalic acid is widely reported in the literature as one of the major components of organic aerosol. It has been reported as both a product of primary emissions from combustion processes and as a secondary product of atmospheric chemistry. Concentrations of particulate oxalate have been measured at a UK urban site (500 daily samples) and for a more limited period simultaneously at a rural site (100 samples) in the fine (less than 2.5 μm) and coarse (2.5-10 μm) size fractions. Full size distributions have also been measured by sampling with a MOUDI cascade impactor. Average concentrations of oxalate sampled over different intervals in PM10 are 0.04 ± 0.03 μg m-3 at the rural site and 0.06 ± 0.05 μg m-3 at the urban background site, broadly comparable with measurements from other European locations. During the period of simultaneous sampling at the urban and rural site, concentrations were very similar and the inter-site correlation in the PM2.5 fraction for oxalate (r = 0.45; p < 0.001) was appreciably weaker than that for sulphate and nitrate (r = 0.82 and 0.84, respectively). Nonetheless, the data clearly point to a predominantly secondary source of oxalate at these sites. Possible contributions from road traffic and woodsmoke appear to be very small. In the larger urban dataset, oxalate in PM2.5 was correlated significantly (p < 0.01) with sulphate (r = 0.60), nitrate (r = 0.48) and secondary organic carbon (r = 0.25). Clustering of air mass back trajectories demonstrates the importance of advection from mainland Europe. The size distribution of oxalate at the urban site showed a major mode at around 0.55 μm and a minor mode at around 1.5 μm in the mass distribution. The former mode is similar to that for sulphate suggesting either a similar in-cloud formation mechanism, or cloud processing of oxalate and sulphate after formation in homogeneous reaction processes.

High-temperature corrosion of metals in the salt and metallic melts containing rare earths

NASA Astrophysics Data System (ADS)

Karpov, V. V.; Abramov, A. V.; Zhilyakov, A. Yu.; Belikov, S. V.; Volkovich, V. A.; Polovov, I. B.; Rebrin, O. I.

2016-09-01

A complex of independent methods was employed to study the corrosion resistance of molybdenum, zirconium, tantalum and tungsten in chloride, chloride-fluoride and fluoride-oxide melts based on LiCl, CaCl2, NaCl- KCl, LiF, and containing rare earths. Tests were conducted for 30 h at 750-1050 °C. The metals showed excellent corrosion resistance in fused chlorides (the corrosion rates were below 0.0005 g/(m2 h). Despite the presence of chemically active fluoride ions in the chloride-fluoride melts, the metals studied also showed very low corrosion rates, except molybdenum, for which the rate of corrosion was 0,8 g/(m2 h). The corrosion resistance of tantalum was considerably reduced in the fluoride-oxide melts; the corrosion rate was over 1 g/(m2 h) corresponding to the 8-th grade of stability and placing tantalum to the group of "low stability" materials.

Alkaline and alkaline earth metal phosphate halides and phosphors

DOEpatents

Lyons, Robert Joseph; Setlur, Anant Achyut; Cleaver, Robert John

2012-11-13

Compounds, phosphor materials and apparatus related to nacaphite family of materials are presented. Potassium and rubidium based nacaphite family compounds and phosphors designed by doping divalent rare earth elements in the sites of alkaline earth metals in the nacaphite material families are descried. An apparatus comprising the phosphors based on the nacaphite family materials are presented herein. The compounds presented is of formula A.sub.2B.sub.1-yR.sub.yPO.sub.4X where the elements A, B, R, X and suffix y are defined such that A is potassium, rubidium, or a combination of potassium and rubidium and B is calcium, strontium, barium, or a combination of any of calcium, strontium and barium. X is fluorine, chlorine, or a combination of fluorine and chlorine, R is europium, samarium, ytterbium, or a combination of any of europium, samarium, and ytterbium, and y ranges from 0 to about 0.1.

YfdW and YfdU Are Required for Oxalate-Induced Acid Tolerance in Escherichia coli K-12

PubMed Central

Fontenot, Elise M.; Ezelle, Karen E.; Gabreski, Lauren N.; Giglio, Eleanor R.; McAfee, John M.; Mills, Alexandria C.; Qureshi, Maryam N.; Salmon, Kristin M.

2013-01-01

Escherichia coli has several mechanisms for surviving low-pH stress. We report that oxalic acid, a small-chain organic acid (SCOA), induces a moderate acid tolerance response (ATR) in two ways. Adaptation of E. coli K-12 at pH 5.5 with 50 mM oxalate and inclusion of 25 mM oxalate in pH 3.0 minimal challenge medium separately conferred protection, with 67% ± 7% and 87% ± 17% survival after 2 h, respectively. The combination of oxalate adaptation and oxalate supplementation in the challenge medium resulted in increased survival over adaptation or oxalate in the challenge medium alone. The enzymes YfdW, a formyl coenzyme A (CoA) transferase, and YfdU, an oxalyl-CoA decarboxylase, are required for the adaptation effect but not during challenge. Unlike other SCOAs, this oxalate ATR is not a part of the RpoS regulon but appears to be linked to the signal protein GadE. We theorize that this oxalate ATR could enhance the pathogenesis of virulent E. coli consumed with oxalate-containing foods like spinach. PMID:23335415

Calcium Oxalate Accumulation in Malpighian Tubules of Silkworm (Bombyx mori)

NASA Astrophysics Data System (ADS)

Wyman, Aaron J.; Webb, Mary Alice

2007-04-01

Silkworm provides an ideal model system for study of calcium oxalate crystallization in kidney-like organs, called Malpighian tubules. During their growth and development, silkworm larvae accumulate massive amounts of calcium oxalate crystals in their Malpighian tubules with no apparent harm to the organism. This manuscript reports studies of crystal structure in the tubules along with analyses identifying molecular constituents of tubule exudate.

In-cloud oxalate formation in the global troposphere: a 3-D modeling study

NASA Astrophysics Data System (ADS)

Myriokefalitakis, S.; Tsigaridis, K.; Mihalopoulos, N.; Sciare, J.; Nenes, A.; Kawamura, K.; Segers, A.; Kanakidou, M.

2011-06-01

Organic acids attract increasing attention as contributors to atmospheric acidity, secondary organic aerosol mass and aerosol hygroscopicity. Oxalic acid is globally the most abundant dicarboxylic acid, formed via chemical oxidation of gas-phase precursors in the aqueous phase of aerosols and droplets. Its lifecycle and atmospheric global distribution remain highly uncertain and are the focus of this study. The first global spatial and temporal distribution of oxalate, simulated using a state-of-the-art aqueous-phase chemical scheme embedded within the global 3-dimensional chemistry/transport model TM4-ECPL, is here presented. The model accounts for comprehensive gas-phase chemistry and its coupling with major aerosol constituents (including secondary organic aerosol). Model results are consistent with ambient observations of oxalate at rural and remote locations (slope = 1.16 ± 0.14, r2 = 0.36, N = 114) and suggest that aqueous-phase chemistry contributes significantly to the global atmospheric burden of secondary organic aerosol. In TM4-ECPL most oxalate is formed in-cloud and less than 5 % is produced in aerosol water. About 62 % of the oxalate is removed via wet deposition, 30 % by in-cloud reaction with hydroxyl radical, 4 % by in-cloud reaction with nitrate radical and 4 % by dry deposition. The in-cloud global oxalate net chemical production is calculated to be about 21-37 Tg yr-1 with almost 79 % originating from biogenic hydrocarbons, mainly isoprene. This condensed phase net source of oxalate in conjunction with a global mean turnover time against deposition of about 5 days, maintain oxalate's global tropospheric burden of 0.2-0.3 Tg, i.e. 0.05-0.1 Tg-C that is about 5-9 % of model-calculated water soluble organic carbon burden.

A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

PubMed

Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

2016-08-01

Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst.

Dual Functionalization of White Phosphorus: Formation, Characterization, and Reactivity of Rare-Earth-Metal Cyclo-P3 Complexes.

PubMed

Du, Shanshan; Yin, Jianhao; Chi, Yue; Xu, Ling; Zhang, Wen-Xiong

2017-12-11

The [3+1] fragmentation reaction of rare-earth metallacyclopentadienes 1 a-c with 0.5 equivalents of P 4 affords a series of rare-earth metal cyclo-P 3 complexes 2 a-c and a phospholyl anion 3. 2 a-c demonstrate an unusual η 3 coordination mode with one P-P bond featuring partial π-bonding character. 2 a-c are the first cyclo-P 3 complexes of rare-earth metals, and also the first organo-substituted polyphosphides in the category of Group 3 and f-block elements. Rare-earth metallacyclopentadienes play a dual role in the combination of aromatization and Diels-Alder reaction. Compounds 2 a-c can coordinate to one or two [W(CO) 5 ] units, yielding 4 a-c or 5 c, respectively. Furthermore, oxidation of 2 a with p-benzoquinone produces its corresponding phospholyllithium and regenerated P 4 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Kimchi Fermentation on Oxalate Levels in Silver Beet (Beta vulgaris var. cicla)

PubMed Central

Wadamori, Yukiko; Vanhanen, Leo; Savage, Geoffrey P.

2014-01-01

Total, soluble and insoluble oxalates were extracted and analyzed by high performance liquid chromatography (HPLC) following the preparation of kimchi using silver beet (Beta vulgaris var. cicla) stems and leaves. As silver beet contains high oxalate concentrations and consumption of high levels can cause the development of kidney stones in some people, the reduction of oxalate during preparation and fermentation of kimchi was investigated. The silver beet stems and leaves were soaked in a 10% brine solution for 11 h and then washed in cold tap water. The total, soluble and insoluble oxalate contents of the silver beet leaves were reduced by soaking in brine, from 4275.81 ± 165.48 mg/100 g to 3709.49 ± 216.51 mg/100 g fresh weight (FW). Fermenting the kimchi for 5 days at 19.3 ± 0.8 °C in 5 L ceramic jars with a water airtight seal resulted in a mean 38.50% reduction in total oxalate content and a mean 22.86% reduction in soluble oxalates. The total calcium content was essentially the same before and after the fermentation of the kimchi (mean 296.1 mg/100 g FW). The study showed that fermentation of kimchi significantly (p < 0.05) reduced the total oxalate concentration in the initial mix from 609.32 ± 15.69 to 374.71 ± 7.94 mg/100 g FW in the final mix which led to a 72.3% reduction in the amount of calcium bound to insoluble oxalate. PMID:28234318

Oxalate Content of Different Drinkable Dilutions of Tea Infusions after Different Brewing Times

PubMed Central

Lotfi Yagin, Neda; Mahdavi, Reza; Nikniaz, Zeinab

2012-01-01

Background: The aims of this study were to determine the effect of different brewing times and diluting on oxalate content of loose-packed black teas consumed in Tabriz, Iran. Methods: The oxalate content of black teas after brewing for 5, 10, 15, 30, 60 minutes was measured in triplicate by enzymatic assay. In order to attain the most acceptable dilution of tea infusions, tea samples which were brewed for 15, 30 and 60 minutes were diluted two (120 ml), three (80 ml) and four (60 ml) times respectively. Results: There was a stepwise increase in oxalate concentrations associated with increased brewing times (P< 0.001) with oxalate contents ranging from 4.4 mg/240 ml for the 5 min to 6.3 mg/240 ml for 60 min brewing times, respectively. There were significant differences between the mean oxalate content of different dilutions after brewing for 15, 30 and 60 minutes (P< 0.001). Conclusion: The oxalate content of Iranian consumed black tea after different brewing times and different dilution was below the recommended levels. Therefore, it seems that consumption of black tea several times per day would not pose significant health risk in kidney stone patients and susceptible individuals. PMID:24688937

Mineralogical basis for the interpretation of multi-element (ICP-AES), oxalic acid, and aqua regia partial digestions of stream sediments for reconnaissance exploration geochemistry

USGS Publications Warehouse

Church, S.E.; Mosier, E.L.; Motooka, J.M.

1987-01-01

We have applied partial digestion procedures, primarily oxalic acid and aqua regia leaches, to several regional geochemical reconnaissance studies carried out using Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) analytical methods. We have chosen to use these two acids because the oxalic acid primarily attacks those compounds formed during secondary geochemical processes, whereas aqua regia will digest the primary sulfide phases as well as secondary phases. Application of the partial digestion technique has proven superior to total digestion because the concentration of metals in hydromorphic compounds and the sulfides is enhanced relative to the metals bound in the unattacked silicate phases. The aqua regia digestion attacks and leaches metals from the mafic chain silicates and the phyllosilicates (coordination number of VI or more), yielding a characteristic geochemical signature, but does not leach appreciable metal from many other silicates. In order to interpret the results from these leach studies, we have initiated an investigation of a large suite of hand-picked mineral separates. The study includes analyses of about two hundred minerals representing the common rock-forming minerals as well as end-member compositions of various silicates, oxides, sulfides, carbonates, sulfates, and some vanadates, molybdates, tungstates, and phosphates. The objective of this study is to evaluate the effect of leaching by acids of particular lattice sites in specific mineral structures. ?? 1987.

An easy access to nanocrystalline alkaline earth metal fluorides - just by shaking

NASA Astrophysics Data System (ADS)

Dreger, M.; Scholz, G.; Kemnitz, E.

2012-04-01

High energy ball milling as fast, direct and solvent free method allows an easy access to nanocrystalline alkaline earth metal fluorides MF2 (M: Mg, Ca, Sr, Ba). Comparable metal sources (acetates, carbonates, hydroxides, alkoxides) were used for the reaction with NH4F as fluorinating agent. Even very simple manual shaking experiments between NH4F and the corresponding hydroxides in the stoichiometric ratio (M:F = 1:2, M: Ca, Sr, Ba) give phase pure fluorides. Moreover, comparable classical thermal reactions in closed crucibles at higher temperatures provide phase pure crystalline fluorides in nearly all cases as well.

Synthesis of Oxides Containing Transition Metals

DTIC Science & Technology

1990-07-09

metal oxide single crystals by the electrolysis of molten salts containing mixtures of the appropriate oxides. Andreiux and Bozon (33-34) were able to...examples of unusual transition metal oxides which can be prepared (usually as single crystals) by electrolysis of fused salts . Summary The methods of...ferrites with the composition MFe 204 involved the thermal decomposition of oxalate (3) or pyridinate salts (1). The synthesis of ferrites from mixed

Effect of animal and vegetable protein intake on oxalate excretion in idiopathic calcium stone disease.

PubMed

Marangella, M; Bianco, O; Martini, C; Petrarulo, M; Vitale, C; Linari, F

1989-04-01

Oxalate excretion was measured in healthy subjects and idiopathic calcium stone-formers on dietary regimens which differed in the type and amount of protein allowed; 24-h urine collections were obtained from 41 practising vegetarians and 40 normal persons on a free, mixed, "mediterranean" diet. Twenty idiopathic calcium stone-formers were also studied while on two low calcium, low oxalate diets which differed in that animal protein was high in one and restricted in the other. Vegetarians had higher urinary oxalate levels than controls and although the calcium levels were markedly lower, urinary saturation with calcium/oxalate was significantly higher. This mild hypercalciuria was interpreted as being secondary to both a higher intake and increased fractional intestinal absorption of oxalate. Changing calcium stone-formers from a high to a low animal protein intake produced a significant decrease in calcium excretion but there was no variation in urinary oxalate. As a result, the decrease in calcium oxalate saturation was only marginal and not significant. It was concluded that dietary animal protein has a minimal effect on oxalate excretion. Mild hyperoxaluria of idiopathic calcium stone disease is likely to be intestinal in origin. Calcium stone-formers should be advised to avoid an excess of animal protein but the risks of a vegetable-rich diet should also be borne in mind.

Oxalic acid biosynthesis is encoded by an operon in Burkholderia glumae

USDA-ARS?s Scientific Manuscript database

Although the biosynthesis of oxalic acid is known to occur in a number of bacteria, the mechanism(s) regulating its production remains largely unknown. To date, there is no report on the identification of an oxalic acid biosynthetic pathway gene from bacteria. In an attempt to identify such a gene...

Biological Control of Meloidogyne incognita by Aspergillus niger F22 Producing Oxalic Acid

PubMed Central

Jang, Ja Yeong; Choi, Yong Ho; Shin, Teak Soo; Kim, Tae Hoon; Shin, Kee-Sun; Park, Hae Woong; Kim, Young Ho; Kim, Hun; Choi, Gyung Ja; Jang, Kyoung Soo; Cha, Byeongjin; Kim, In Seon; Myung, Eul Jae

2016-01-01

Restricted usage of chemical nematicides has led to development of environmentally safe alternatives. A culture filtrate of Aspergillus niger F22 was highly active against Meloidogyne incognita with marked mortality of second-stage juveniles (J2s) and inhibition of egg hatching. The nematicidal component was identified as oxalic acid by organic acid analysis and gas chromatography-mass spectroscopy (GC-MS). Exposure to 2 mmol/L oxalic acid resulted in 100% juvenile mortality at 1 day after treatment and suppressed egg hatching by 95.6% at 7 days after treatment. Oxalic acid showed similar nematicidal activity against M. hapla, but was not highly toxic to Bursaphelenchus xylophilus. The fungus was incubated on solid medium and dried culture was used for preparation of a wettable powder-type (WP) formulation as an active ingredient. Two WP formulations, F22-WP10 (ai 10%) and oxalic acid-WP8 (ai 8%), were prepared using F22 solid culture and oxalic acid. In a field naturally infested with M. incognita, application of a mixture of F22-WP10 + oxalic acid-WP8 at 1,000- and 500-fold dilutions significantly reduced gall formation on the roots of watermelon plants by 58.8 and 70.7%, respectively, compared to the non-treated control. The disease control efficacy of the mixture of F22-WP10 + oxalic acid-WP8 was significantly higher than that of a chemical nematicide, Sunchungtan (ai 30% fosthiazate). These results suggest that A. niger F22 can be used as a microbial nematicide for the control of root-knot nematode disease. PMID:27258452

Biological Control of Meloidogyne incognita by Aspergillus niger F22 Producing Oxalic Acid.

PubMed

Jang, Ja Yeong; Choi, Yong Ho; Shin, Teak Soo; Kim, Tae Hoon; Shin, Kee-Sun; Park, Hae Woong; Kim, Young Ho; Kim, Hun; Choi, Gyung Ja; Jang, Kyoung Soo; Cha, Byeongjin; Kim, In Seon; Myung, Eul Jae; Kim, Jin-Cheol

2016-01-01

Restricted usage of chemical nematicides has led to development of environmentally safe alternatives. A culture filtrate of Aspergillus niger F22 was highly active against Meloidogyne incognita with marked mortality of second-stage juveniles (J2s) and inhibition of egg hatching. The nematicidal component was identified as oxalic acid by organic acid analysis and gas chromatography-mass spectroscopy (GC-MS). Exposure to 2 mmol/L oxalic acid resulted in 100% juvenile mortality at 1 day after treatment and suppressed egg hatching by 95.6% at 7 days after treatment. Oxalic acid showed similar nematicidal activity against M. hapla, but was not highly toxic to Bursaphelenchus xylophilus. The fungus was incubated on solid medium and dried culture was used for preparation of a wettable powder-type (WP) formulation as an active ingredient. Two WP formulations, F22-WP10 (ai 10%) and oxalic acid-WP8 (ai 8%), were prepared using F22 solid culture and oxalic acid. In a field naturally infested with M. incognita, application of a mixture of F22-WP10 + oxalic acid-WP8 at 1,000- and 500-fold dilutions significantly reduced gall formation on the roots of watermelon plants by 58.8 and 70.7%, respectively, compared to the non-treated control. The disease control efficacy of the mixture of F22-WP10 + oxalic acid-WP8 was significantly higher than that of a chemical nematicide, Sunchungtan (ai 30% fosthiazate). These results suggest that A. niger F22 can be used as a microbial nematicide for the control of root-knot nematode disease.

Synthesis of calcium oxalate crystals in culture medium irradiated with non-equilibrium atmospheric-pressure plasma

NASA Astrophysics Data System (ADS)

Kurake, Naoyuki; Tanaka, Hiromasa; Ishikawa, Kenji; Nakamura, Kae; Kajiyama, Hiroaki; Kikkawa, Fumitaka; Mizuno, Masaaki; Yamanishi, Yoko; Hori, Masaru

2016-09-01

Octahedral particulates several tens of microns in size were synthesized in a culture medium irradiated through contact with a plume of non-equilibrium atmospheric-pressure plasma (NEAPP). The particulates were identified in the crystalline phase as calcium oxalate dihydrate (COD). The original medium contained constituents such as NaCl, d-glucose, CaCl2, and NaHCO3 but not oxalate or oxalic acid. The oxalate was clearly synthesized and crystallized in the medium as thermodynamically unstable COD crystals after the NEAPP irradiation.

Chronic dietary oxalate nephropathy after intensive dietary weight loss regimen

PubMed Central

Khneizer, Gebran; Al-Taee, Ahmad; Mallick, Meher S; Bastani, Bahar

2017-01-01

Background: Hyperoxaluria has been associated with nephrolithiasis as well as acute and chronic kidney disease. We present a case of end stage renal failure caused by excessive dietary oxalate intake in a dietary weight loss regimen. Case Presentation: A 51-year-old Caucasian male with the past medical history of type 2 diabetes mellitus, gout, hypertension and morbid obesity was referred to the primary care clinic after being found pale and easily fatigued. The patient had lost 36 kg over a 7-month period by implementing exercise and intense dietary measures that included 6 meals of spinach, kale, berries, and nuts. Physical examination revealed a blood pressure of 188/93 mm Hg with sunken eyes and dry mucus membranes. Laboratory workup was notable for blood urea nitrogen of 122 mg/dL, creatinine of 12 mg/dL, and estimated glomerular filtration rate (eGFR) of 4.4 mL/min/1.73m2. Patient denied any history of renal disease or renal stones, or taking herbal products, non-steroidal anti-inflammatory drugs, antifreeze (ethylene glycol), or any type of "diet pills." Family history was unremarkable for any renal diseases. After failing intravenous fluid resuscitation, patient was started on maintenance hemodialysis. Abdominal imaging was consistent with chronic renal parenchymal disease with no evidence of nephrolithiasis. Renal biopsy revealed numerous polarized oxalate crystal deposition and diabetic nephropathy class IIA. At this point the patient was instructed to adopt a low oxalate diet. A 24-hour urine collection was remarkable for pH 4.7, citrate <50 mg, and oxalate 46 mg. Importantly, serum oxalate level was undetectable. Repeat renal biopsy 5 months later while patient was still on maintenance hemodialysis revealed persistence of extensive oxalate crystal deposition. Patient has been referred for evaluation for renal transplantation. Conclusions: Clinicians need to maintain a high index of suspicion for dietary hyperoxaluria as a potential etiology for acute or

The effects of copper proximity on oxalate production in Fibroporia radiculosa

Treesearch

Katie M. Jenkins; Carol A. Clausen; Frederick Green III

2014-01-01

Copper remains a key component used in wood preservatives available today. However, the observed tolerance of several critical wood rotting organisms continues to be problematic. Tolerance to copper has been linked to the production and accumulation of oxalate, which precipitates copper into insoluble copper-oxalate crystals, thus inactivating copper ions. The purpose...

PRETREATING URANIUM FOR METAL PLATING

DOEpatents

Wehrmann, R.F.

1961-05-01

A process is given for anodically treating the surface of uranium articles, prior to metal plating. The metal is electrolyzed in an aqueous solution of about 10% polycarboxylic acid, preferably oxalic acid, from 1 to 5% by weight of glycerine and from 1 to 5% by weight of hydrochloric acid at from 20 to 75 deg C for from 30 seconds to 15 minutes. A current density of from 60 to 100 amperes per square foot is used.

Effects of pH on frog gustatory responses to chloride salts of alkali-metal and alkali-earth-metal.

PubMed

Kumai, T; Nomura, H

1980-01-01

The pH effects on frog gustatory responses to alkali-metal and alkali-earth-metal chloride salts were examined using single fungi-form papilla preparations. Responses to 0.1-0.5 M NaCl were clearly dependent upon the pH of the stimulating solutions. The responses increased as the pH decreased from 6.5 to 4.5 and were almost completely suppressed at pH's above 6.5. There was no significant difference in the pH dependency of the response among alkali-metal chlorides. HCl solutions elicited only a poor response under conditions in which the water response was suppressed by the simultaneous presence of a low NaCl concentration. Responses to alkali-earth-metal chlorides varied in their pH dependency. Response to CaCl2 was slightly affected by pH changes from 4.5 to 9.0, response to SrCl2 was considerably suppressed in the alkaline region, and responses to BaCl2 and MgCl2 were strongly suppressed at pH's above 6.5. BeCl2 solutions showed less marked stimulating effects over the pH range tested. The differences in pH dependency described above suggest the existence of two kinds of receptor sites, one being pH-insensitive sites responsible for the calcium response and the other pH-sensitive sites responsible for the sodium response. A cross-adaptation test appeared to support this possibility. Assuming that the pH effect mentioned is related to changes in the state of ionization of the receptor molecule, the pKa of the ionizable group responsible for the sodium response was determined to be approximately 5.5.

Nanoscale observations of the effect of citrate on calcium oxalate precipitation on calcite surfaces.

NASA Astrophysics Data System (ADS)

Burgos-Cara, Alejandro; Ruiz-Agudo, Encarnacion; Putnis, Christine V.

2016-04-01

Calcium oxalate (CaC2O4ṡxH2O) minerals are naturally occurring minerals found in fossils, plants, kidney stones and is a by-product in some processes such as paper, food and beverage production [1,2]. In particular, calcium oxalate monohydrate phase (COM) also known as whewellite (CaC2O4ṡH2O), is the most frequently reported mineral phase found in urinary and kidney stones together with phosphates. Organic additives are well known to play a key role in the formation of minerals in both biotic and abiotic systems, either facilitating their precipitation or hindering it. In this regard, recent studies have provided direct evidence demonstrating that citrate species could enhance dissolution of COM and inhibit their precipitation. [3,4] The present work aims at evauate the influence of pH, citrate and oxalic acid concentrations in calcium oxalate precipitation on calcite surfaces (Island Spar, Chihuahua, Mexico) through in-situ nanoscale observation using in situ atomic force microscopy (AFM, Multimode, Bruker) in flow-through experiments. Changes in calcium oxalate morphologies and precipitated phases were observed, as well as the inhibitory effect of citrate on calcium oxalate precipitation, which also lead to stabilization an the amorphous calcium oxalate phase. [1] K.D. Demadis, M. Öner, Inhibitory effects of "green"additives on the crystal growth of sparingly soluble salts, in: J.T. Pearlman (Ed.), Green Chemistry Research Trends, Nova Science Publishers Inc., New York, 2009, pp. 265-287. [2] M. Masár, M. Zuborová, D. Kaniansky, B. Stanislawski, Determination of oxalate in beer by zone electrophoresis on a chip with conductivity detection, J. Sep. Sci. 26 (2003) 647-652. [3] Chutipongtanate S, Chaiyarit S, Thongboonkerd V. Citrate, not phosphate, can dissolve calcium oxalate monohydrate crystals and detach these crystals from renal tubular cells. Eur J Pharmacol 2012;689:219-25. [4] Weaver ML, Qiu SR, Hoyer JR, Casey WH, Nancollas GH, De Yoreo JJ

The Electronic Structure and Optical Properties of Anatase TiO2 with Rare Earth Metal Dopants from First-Principles Calculations

PubMed Central

Xie, Kefeng; Jia, Qiangqiang; Wang, Yizhe; Zhang, Wenxue; Xu, Jingcheng

2018-01-01

The electronic and optical properties of the rare earth metal atom-doped anatase TiO2 have been investigated systematically via density functional theory calculations. The results show that TiO2 doped by Ce or Pr is the optimal choice because of its small band gap and strong optical absorption. Rare earth metal atom doping induces several impurity states that tune the location of valence and conduction bands and an obvious lattice distortion that should reduce the probability of electron–hole recombination. This effect of band change originates from the 4f electrons of the rare earth metal atoms, which leads to an improved visible light absorption. This finding indicates that the electronic structure of anatase TiO2 is tuned by the introduction of impurity atoms. PMID:29364161

Plant calcium oxalate crystal formation, function, and its impact on human health

USDA-ARS?s Scientific Manuscript database

Crystals of calcium oxalate have been observed among members from most taxonomic groups of photosynthetic organisms ranging from the smallest algae to the largest trees. The biological roles for calcium oxalate crystal formation in plant growth and development include high capacity calcium regulatio...

The production of (14C) oxalate during the metabolism of (14C) carbohydrates in isolated rat hepatocytes.

PubMed

Rofe, A M; James, H M; Bais, R; Edwards, J B; Conyers, R A

1980-04-01

Oxalate (14C) was produced during the metabolism of (U-14C) carbohydrates in hepatocytes isolated from normal rats. At 10 mM, the order of oxalate production was fructose > glycerol > xylitol > sorbitol greater than or equal to glucose in the ratio 10 : 4 : 3 : 1 : 1. This difference between oxalate production from fructose and glucose was reflected in their rates of utilisation, glucose being poorly metabolised in hepatocytes from fasted rats. Fructose was rapidly metabolised, producing glucose, lactate and pyruvate as the major metabolites. Glycerol, xylitol and sorbitol were metabolised at half the rate of fructose, the major metabolites being glucose, lactate and glycerophosphate. The marked similarity in the pattern of intermediary metabolites produced by these polyols was not, however, reflected in the rates of oxalate production. Hepatic polyol metabolism resulted in high levels of cytosolic NADH, as indicated by elevated lactate : pyruvate and glycerophosphate : dihydroxyacetone phosphate ratios. The artificial electron acceptor, phenazine methosulphate (PMS) stimulated oxalate production from the polyols, particularly xylitol. In the presence of PMS, the order of oxalate production was fructose greater than or equal to xylitol > glycerol > sorbitol in the ratio 10 : 10 : 6 : 2. The production of glucose, lactate and pyruvate from the polyols was also stimulated by PMS, whereas the general metabolism of fructose, including oxalate production, was little affected. Oxalate (14C) was produced from (1-14C), (2-14C) and (6-14C) but not (3,4-14C) glucose in hepatocytes isolated from non-fasted, pyridoxine-deficient rats. Whilst this labelling pattern is consistent with oxalate being produced by a number of pathways, it is suggested that metabolism via hydroxypyruvate is a major route for oxalate production from various carbohydrates, with perhaps the exception of xylitol, which appears to have an alternative mechanism for oxalate production. The observation that

Reverse engineering the kidney: modelling calcium oxalate monohydrate crystallization in the nephron.

PubMed

Borissova, A; Goltz, G E; Kavanagh, J P; Wilkins, T A

2010-07-01

Crystallization of calcium oxalate monohydrate in a section of a single kidney nephron (distal convoluted tubule) is simulated using a model adapted from industrial crystallization. The nephron fluid dynamics is represented as a crystallizer/separator series with changing volume to allow for water removal along the tubule. The model integrates crystallization kinetics and crystal size distribution and allows the prediction of the calcium oxalate concentration profile and the nucleation and growth rates. The critical supersaturation ratio for the nucleation of calcium oxalate crystals has been estimated as 2 and the mean crystal size as 1 mum. The crystal growth order, determined as 2.2, indicates a surface integration mechanism of crystal growth and crystal growth dispersion. The model allows the exploration of the effect of varying the input calcium oxalate concentration and the rate of water extraction, simulating real life stressors for stone formation such as dietary loading and dehydration.

Determining the Structure of Oxalate Anion Using Infrared and Raman Spectroscopy Coupled with Gaussian Calculations

ERIC Educational Resources Information Center

Peterson, Karen I.; Pullman, David P.

2016-01-01

A laboratory project for the upper-division physical chemistry laboratory is described, and it combines IR and Raman spectroscopies with Gaussian electronic structure calculations to determine the structure of the oxalate anion in solid alkali oxalates and in aqueous solution. The oxalate anion has two limiting structures whose vibrational spectra…

Acute oxalate nephropathy due to ‘Averrhoa bilimbi’ fruit juice ingestion

PubMed Central

Bakul, G.; Unni, V. N.; Seethaleksmy, N. V.; Mathew, A.; Rajesh, R.; Kurien, G.; Rajesh, J.; Jayaraj, P. M.; Kishore, D. S.; Jose, P. P.

2013-01-01

Irumban puli (Averrhoa bilimbi) is commonly used as a traditional remedy in the state of Kerala. Freshly made concentrated juice has a very high oxalic acid content and consumption carries a high risk of developing acute renal failure (ARF) by deposition of calcium oxalate crystals in renal tubules. Acute oxalate nephropathy (AON) due to secondary oxalosis after consumption of Irumban puli juice is uncommon. AON due to A. bilimbi has not been reported before. We present a series of ten patients from five hospitals in the State of Kerala who developed ARF after intake of I. puli fruit juice. Seven patients needed hemodialysis whereas the other three improved with conservative management. PMID:23960349

Effect of oxalate on the dissolution rates of oligoclase and tremolite (journal version)

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

Mast, M.A.; Drever, J.I.

1987-01-01

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22 deg C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of releasemore » of Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si. The rate of dissolution of tremolite is independent of pH over the pH range 2-5, and decreases at higher pH. The rate of dissolution of oligoclase was independent of pH over the pH range 4-9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.« less

Selective Rac1 inhibition protects renal tubular epithelial cells from oxalate-induced NADPH oxidase-mediated oxidative cell injury

PubMed Central

Thamilselvan, Vijayalakshmi; Menon, Mani

2013-01-01

Oxalate-induced oxidative cell injury is one of the major mechanisms implicated in calcium oxalate nucleation, aggregation and growth of kidney stones. We previously demonstrated that oxalate-induced NADPH oxidase-derived free radicals play a significant role in renal injury. Since NADPH oxidase activation requires several regulatory proteins, the primary goal of this study was to characterize the role of Rac GTPase in oxalate-induced NADPH oxidase-mediated oxidative injury in renal epithelial cells. Our results show that oxalate significantly increased membrane translocation of Rac1 and NADPH oxidase activity of renal epithelial cells in a time-dependent manner. We found that NSC23766, a selective inhibitor of Rac1, blocked oxalate-induced membrane translocation of Rac1 and NADPH oxidase activity. In the absence of Rac1 inhibitor, oxalate exposure significantly increased hydrogen peroxide formation and LDH release in renal epithelial cells. In contrast, Rac1 inhibitor pretreatment, significantly decreased oxalate-induced hydrogen peroxide production and LDH release. Furthermore, PKC α and δ inhibitor, oxalate exposure did not increase Rac1 protein translocation, suggesting that PKC resides upstream from Rac1 in the pathway that regulates NADPH oxidase. In conclusion, our data demonstrate for the first time that Rac1-dependent activation of NADPH oxidase might be a crucial mechanism responsible for oxalate-induced oxidative renal cell injury. These findings suggest that Rac1 signaling plays a key role in oxalate-induced renal injury, and may serve as a potential therapeutic target to prevent calcium oxalate crystal deposition in stone formers and reduce recurrence. PMID:21814770

Characterization of calcium oxalate biominerals in Pereskia species (Cactaceae).

PubMed

Monje, Paula V; Baran, Enrique J

2009-01-01

Calcium oxalate druses were isolated from the stems and leaves of six Pereskioideae family members and investigated by infrared spectroscopy, showing that in all samples the biomineral was present in the form of whewellite, CaC2O4 x H2O. As Pereskia is thought to represent the "ancestral" condition of the leafless stem-succulent cacti, these results suggest that the biomineralization of calcium oxalate in Cactaceae represents a primitive characteristic of the group and also support a close genetic relationship between Pereskia and Opuntia.

Metamagnetism and weak ferromagnetism in nickel (II) oxalate crystals

NASA Astrophysics Data System (ADS)

Romero-Tela, E.; Mendoza, M. E.; Escudero, R.

2012-05-01

Microcrystals of orthorhombic nickel (II) oxalate dihydrate were synthesized through a precipitation reaction of aqueous solutions of nickel chloride and oxalic acid. Magnetic susceptibility exhibits a sharp peak at 3.3 K and a broad rounded maximum near 43 K. We associated the lower maximum with a metamagnetic transition that occurs when the magnetic field is about ≥ 3.5 T. The maximum at 43 K is typical of 1D antiferromagnets, whereas weak ferromagnetism behavior was observed in the range of 3.3-43 K.

C-Phycocyanin Confers Protection against Oxalate-Mediated Oxidative Stress and Mitochondrial Dysfunctions in MDCK Cells

PubMed Central

Farooq, Shukkur M.; Boppana, Nithin B.; Asokan, Devarajan; Sekaran, Shamala D.; Shankar, Esaki M.; Li, Chunying; Gopal, Kaliappan; Bakar, Sazaly A.; Karthik, Harve S.; Ebrahim, Abdul S.

2014-01-01

Oxalate toxicity is mediated through generation of reactive oxygen species (ROS) via a process that is partly dependent on mitochondrial dysfunction. Here, we investigated whether C-phycocyanin (CP) could protect against oxidative stress-mediated intracellular damage triggered by oxalate in MDCK cells. DCFDA, a fluorescence-based probe and hexanoyl-lysine adduct (HEL), an oxidative stress marker were used to investigate the effect of CP on oxalate-induced ROS production and membrane lipid peroxidation (LPO). The role of CP against oxalate-induced oxidative stress was studied by the evaluation of mitochondrial membrane potential by JC1 fluorescein staining, quantification of ATP synthesis and stress-induced MAP kinases (JNK/SAPK and ERK1/2). Our results revealed that oxalate-induced cells show markedly increased ROS levels and HEL protein expression that were significantly decreased following pre-treatment with CP. Further, JC1 staining showed that CP pre-treatment conferred significant protection from mitochondrial membrane permeability and increased ATP production in CP-treated cells than oxalate-alone-treated cells. In addition, CP treated cells significantly decreased the expression of phosphorylated JNK/SAPK and ERK1/2 as compared to oxalate-alone-treated cells. We concluded that CP could be used as a potential free radical-scavenging therapeutic strategy against oxidative stress-associated diseases including urolithiasis. PMID:24691130

Effects of potassium oxalate on knoop hardness of etch-and-rinse adhesives.

PubMed

Silva, S M A; Malacarne-Zanon, J; Carvalho, R M; Alves, M C; De Goes, M F; Anido-Anido, A; Carrilho, M R

2012-01-01

The objective of this study was to determine whether the hardness of etch-and-rinse adhesives may be affected by the pretreatment of acid-etched dentin with potassium oxalate desensitizer. Unerupted human third molars were cut into crown segments by removing the occlusal enamel and roots. The pulp chamber of these crown segments was connected to a syringe barrel filled with phosphate-buffered saline so that the moisture of dentin was maintained during the bonding procedures. Three etch-and-rinse adhesives-two two-step systems (Adper Single Bond 2 [SB], One-Step [OS]) and one three-step system (Adper Scotchbond Multi-Purpose [MP])-were applied to acid-etched dentin that had been treated (experimental groups) or not (control groups) with potassium oxalate (BisBlock). The Knoop hardness (KHN) of adhesives was taken at different sites of the outer surface of the adhesive-bonded dentin. The KHN of the three tested adhesives applied to acid-etched dentin treated with potassium oxalate was significantly lower than that exhibited by the respective controls (not treated with oxalate; p<0.05). Regardless of the adhesive, the treatment with potassium oxalate reduced the adhesives' KHN (p<0.05), with the OS system exhibiting the lowest KHN compared with the MP and SB systems.

Calcium extraction from brine water and seawater using oxalic acid

NASA Astrophysics Data System (ADS)

Natasha, Nadia Chrisayu; Lalasari, Latifa Hanum

2017-01-01

Calcium can be extracted not only from rocks but also from natural liquor such as seawater and brine water. In order to extract the calcium from seawater and brine water, oxalic acid was used in this research. Effect of variations of the volume of the oxalic acid at a constant concentration in seawater and brine water to produce calcium was investigated. The concentration of oxalic acid was 100 g/l and the variations of its volume were 2 ml, 4 ml, 6 ml, 8 ml, 10 ml, 20 ml, 30 ml, 40 ml, and 50 ml. The used seawater and brine water were firstly evaporated from 100 ml into 50 ml and then the oxalic acid was added into them with mixing to produce the calcium precipitates. The precipitates were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) and the filtrates were analyzed by inductively coupled plasma-optical emission spectrometry (ICP-OES). The SEM analysis showed that the precipitates from brine water were consisted of only calcium compound while from seawater sodium one was also found along with calcium compound. The XRD analysis showed that the calcium was present in the form of calcium oxalate for both seawater and brine water. The ICP-OES analysis of the filtrate from seawater precipitation showed that the its calcium content was decreased from 826.20 ppm to 0.04 ppm while from brine water, it decreased from 170.06 ppm to 1.96 ppm. These results showed that both seawater and brine water have the potential to be a raw material for calcium production.

Antiurolithiatic Potential of Neeri against Calcium-Oxalate Stones by Crystallization Inhibition, Free Radicals Scavenging, and NRK-52E Cell Protection from Oxalate Injury.

PubMed

Goyal, Parveen Kumar; Verma, Santosh Kumar; Sharma, Anil Kumar

2017-10-01

Neeri is a well-established polyherbal formulation prescribed for renal stones by the physicians but has not been experimentally evaluated for its antiurolithiatic potential using cell-lines. This study is aimed to scientifically substantiate the antiurolithiatic effect of Neeri extract (NRE) through calcium oxalate (CaOx) crystallization inhibition, scavenging of free radicals, and protection of renal tubular epithelial NRK-52E cells from oxalate-induced injury. The crystallization inhibition was studied by turbidimetric assay while the free radical scavenging potential was determined for superoxide and nitric oxide (NO) radicals. The cytoprotective effect against oxalate-induced injury was assessed by estimating lactate dehydrogenase (LDH) leakage and determining cell viability using 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. NRE significantly inhibited the CaOx crystallization in a concentration-dependent manner and also scavenged superoxide (IC 50 302.88 μg/ml) and NO (IC 50 300.45 μg/ml) free radicals. It did not show any significant cytotoxicity for NRK-52E cells till the highest dose (500 μg/ml) and found to be safe. When NRK-52E cells, injured by exposing to oxalate crystals for 24 h, were treated with NRE, it appreciably prevented the cell injury in a dose-dependent manner. It significantly decreased the elevated LDH leakage toward normal range and improved renal cell viability (82.37% ± 0.87%), hence, prevented growth and retention of crystals. The experimental findings concluded that Neeri is a potent antiurolithiatic formulation that inhibited CaOx crystallization and prevented tubular retention of crystals by protecting the renal cells against oxalate-induced injury as well as reducing the oxidative stress by scavenging free radicals. Neeri extract significantly ( P < 0.001) inhibited the in vitro crystallization (88.11% ± 7.70%) of calcium oxalateIt reduced oxidative stress by scavenging superoxide and nitric oxide free

Formation of an integrated holding company to produce rare-earth metal articles

NASA Astrophysics Data System (ADS)

Bogdanov, S. V.; Grishaev, S. I.

2013-12-01

The possibility of formation of a Russian holding company for the production of rare-earth metal articles under conditions of its increasing demand on the world market is considered. It is reasonable to ensure stable business operation on the market under conditions of state-private partnership after the fraction of soled products is determined and supported by the competitive advantages of Russian products.

Crystal forms of the hydrogen oxalate salt of o-desmethylvenlafaxine.

PubMed

Dichiarante, Elena; Curzi, Marco; Giaffreda, Stefano L; Grepioni, Fabrizia; Maini, Lucia; Braga, Dario

2015-06-01

To prepare new crystalline forms of the antidepressant o-desmethylvenlafaxine salt as potential new commercial forms and evaluate their physicochemical properties, in particular the dissolution rate. A new hydrogen oxalate salt of o-desmethylvenlafaxine hydrogen oxalate (ODV-OX) was synthesized, and a polymorph screening was performed using different solvents and crystallization conditions. Crystalline forms were characterized by a combination of solid-state techniques: X-ray powder diffraction, differential scanning calorimetry, thermogravimetric analysis, FT-IR spectroscopy and single crystal X-ray diffraction. The stability of all crystalline phases was tested under International Conference on Harmonisation (ICH) conditions (40°C and 75% Relative Humidity (RH)) for 1 week. Dissolution tests were performed on the hydrogen oxalate salt ODV-OX Form 1 and compared with dissolution test on the commercial form of the succinate salt of o-desmethylvenlafaxine. Five crystalline forms of ODV-OX were isolated, namely three hydrated forms (Form 1, Form 2, Form 3) and two anhydrous forms (Form 4 and Form 5). Comparative solubility tests on ODV-OX Form 1 and o-desmethylvenlafaxine succinate evidenced a significant increase in solubility for the hydrogen oxalate salt (142 g/l) with respect to the succinate salt (70 g/l). © 2015 Royal Pharmaceutical Society.

Two New Families of Lanthanide Mixed-Ligand Complexes, Oxalate-Carbonate and Oxalate-Formate: Synthesis and Structure of [Ce(H 2O)] 2(C 2O 4) 2(CO 3)·2.5 H 2O and Ce(C 2O 4)(HCO 2)

NASA Astrophysics Data System (ADS)

Romero, S.; Mosset, A.; Trombe, J. C.

1996-12-01

Two new families of lanthanide complexes associating the ligands oxalate and carbonate or oxalate and formate have been prepared under autogenous pressure at 200°C using a pseudo-hydrothermal method. The two families have been extended to some lanthanides ( Ln): oxalate-carbonate Ln= Ce, Pr, Nd, and Eu; oxalate-formate Ln= La, Ce, and Sm. The starting suspension contains either oxalate or a mixture of oxalate and oxalic acid. The structures have been solved for the element cerium. In both cases, the structure is built up from cerium atoms sharing all their oxygen atoms with oxalate and carbonate or oxalate and formate ligands, thus forming a three-dimensional network. The cerium polyhedra share either faces or edges or corners. The coordination scheme of the oxalate ligands is variable: bischelating, bischelating and monodentate, or bischelating and bismonodentate. The carbonate group acts as a bischelating and bismonodentate ligand while the formate group is chelating and monodentate. The characterization of these two original families by infrared spectra and thermal behavior is presented for some pure phases. A tentative explanation of the synthesis of these two phases will be emphasized.

Highly efficient hydrophosphonylation of aldehydes and unactivated ketones catalyzed by methylene-linked pyrrolyl rare earth metal amido complexes.

PubMed

Zhou, Shuangliu; Wu, Zhangshuan; Rong, Jiewei; Wang, Shaowu; Yang, Gaosheng; Zhu, Xiancui; Zhang, Lijun

2012-02-27

A series of rare earth metal amido complexes bearing methylene-linked pyrrolyl-amido ligands were prepared through silylamine elimination reactions and displayed high catalytic activities in hydrophosphonylations of aldehydes and unactivated ketones under solvent-free conditions for liquid substrates. Treatment of [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) with 2-(2,6-Me(2)C(6)H(3)NHCH(2))C(4)H(3)NH (1, 1 equiv) in toluene afforded the corresponding trivalent rare earth metal amides of formula {(μ-η(5):η(1)):η(1)-2-[(2,6-Me(2)C(6)H(3))NCH(2)](C(4)H(3)N)LnN(SiMe(3))(2)}(2) [Ln=Y (2), Nd (3), Sm (4), Dy (5), Yb (6)] in moderate to good yields. All compounds were fully characterized by spectroscopic methods and elemental analyses. The yttrium complex was also characterized by (1)H NMR spectroscopic analyses. The structures of complexes 2, 3, 4, and 6 were determined by single-crystal X-ray analyses. Study of the catalytic activities of the complexes showed that these rare earth metal amido complexes were excellent catalysts for hydrophosphonylations of aldehydes and unactivated ketones. The catalyzed reactions between diethyl phosphite and aldehydes in the presence of the rare earth metal amido complexes (0.1 mol%) afforded the products in high yields (up to 99%) at room temperature in short times of 5 to 10 min. Furthermore, the catalytic addition of diethyl phosphite to unactivated ketones also afforded the products in high yields of up to 99% with employment of low loadings (0.1 to 0.5 mol%) of the rare earth metal amido complexes at room temperature in short times of 20 min. The system works well for a wide range of unactivated aliphatic, aromatic or heteroaromatic ketones, especially for substituted benzophenones, giving the corresponding α-hydroxy diaryl phosphonates in moderate to high yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production method for making rare earth compounds

DOEpatents

McCallum, R.W.; Ellis, T.W.; Dennis, K.W.; Hofer, R.J.; Branagan, D.J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g., a transition metal and optional boron), and a carbide-forming element (e.g., a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g., Nd{sub 2}Fe{sub 14}B or LaNi{sub 5}) and a carbide of the carbide-forming element are formed.

Production method for making rare earth compounds

DOEpatents

McCallum, R. William; Ellis, Timothy W.; Dennis, Kevin W.; Hofer, Robert J.; Branagan, Daniel J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g. a transition metal and optional boron), and a carbide-forming element (e.g. a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g. Nd.sub.2 Fe.sub.14 B or LaNi.sub.5) and a carbide of the carbide-forming element are formed.

Metal-silicate Partitioning and Its Role in Core Formation and Composition on Super-Earths

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

Schaefer, Laura; Petaev, M. I.; Sasselov, Dimitar D.

We use a thermodynamic framework for silicate-metal partitioning to determine the possible compositions of metallic cores on super-Earths. We compare results using literature values of the partition coefficients of Si and Ni, as well as new partition coefficients calculated using results from laser shock-induced melting of powdered metal-dunite targets at pressures up to 276 GPa, which approaches those found within the deep mantles of super-Earths. We find that larger planets may have little to no light elements in their cores because the Si partition coefficient decreases at high pressures. The planet mass at which this occurs will depend on themore » metal-silicate equilibration depth. We also extrapolate the equations of state (EOS) of FeO and FeSi alloys to high pressures, and present mass–radius diagrams using self-consistent planet compositions assuming equilibrated mantles and cores. We confirm the results of previous studies that the distribution of elements between mantle and core will not be detectable from mass and radius measurements alone. While observations may be insensitive to interior structure, further modeling is sensitive to compositionally dependent properties, such as mantle viscosity and core freeze-out properties. We therefore emphasize the need for additional high pressure measurements of partitioning as well as EOSs, and highlight the utility of the Sandia Z-facilities for this type of work.« less

Calcium oxalate syntheses in a solution containing glucose by the atmospheric pressure plasma irradiation

NASA Astrophysics Data System (ADS)

Kurake, Naoyuki; Tanaka, Hiromasa; Ishikawa, Kenji; Nakamura, Kae; Kajiyama, Hiroaki; Kikkawa, Fumitaka; Mizuno, Masaaki; Yamanishi, Yoko; Hori, Masaru

2016-09-01

The non-equilibrium atmospheric pressure plasma (NEAPP) has been attracted attention because of its characteristic high reactivity even in a low temperature so that various phenomena by the NEAPP such as a sterilization, growth promotion and so forth have been reported around the world. Previously, we reported the NEAPP irradiation generated the calcium oxalate crystals in the medium, which contains 31 kinds of organics and inorganics. The Dulbecco's Modified Eagle Medium (DMEM) which was used in previous study is composed of no oxalate. Interestingly, not only crystallization but also synthesis of the oxalate was occurred by the NEAPP irradiation. Also the crystallization details were analyzed with the X-ray diffraction (XRD). In this study, we have clarified the mechanism on the crystallization due that D-glucose, calcium ion and bicarbonate ions are minimum essential components. The oxalate synthesis was proved by the gas chromatography and mass spectrometer (GC-MS). Finally, we conclude that a supersaturation of oxalic acid synthesized in those 3 species by the NEAPP.

The Gastrointestinal Tract of the White-Throated Woodrat (Neotoma albigula) Harbors Distinct Consortia of Oxalate-Degrading Bacteria

PubMed Central

Kohl, Kevin D.; Dearing, M. Denise

2014-01-01

The microbiota inhabiting the mammalian gut is a functional organ that provides a number of services for the host. One factor that may regulate the composition and function of gut microbial communities is dietary toxins. Oxalate is a toxic plant secondary compound (PSC) produced in all major taxa of vascular plants and is consumed by a variety of animals. The mammalian herbivore Neotoma albigula is capable of consuming and degrading large quantities of dietary oxalate. We isolated and characterized oxalate-degrading bacteria from the gut contents of wild-caught animals and used high-throughput sequencing to determine the distribution of potential oxalate-degrading taxa along the gastrointestinal tract. Isolates spanned three genera: Lactobacillus, Clostridium, and Enterococcus. Over half of the isolates exhibited significant oxalate degradation in vitro, and all Lactobacillus isolates contained the oxc gene, one of the genes responsible for oxalate degradation. Although diverse potential oxalate-degrading genera were distributed throughout the gastrointestinal tract, they were most concentrated in the foregut, where dietary oxalate first enters the gastrointestinal tract. We hypothesize that unique environmental conditions present in each gut region provide diverse niches that select for particular functional taxa and communities. PMID:24362432

Evidence of a natural marine source of oxalic acid and a possible link to glyoxal

NASA Astrophysics Data System (ADS)

Rinaldi, Matteo; Decesari, Stefano; Carbone, Claudio; Finessi, Emanuela; Fuzzi, Sandro; Ceburnis, Darius; O'Dowd, Colin D.; Sciare, Jean; Burrows, John P.; Vrekoussis, Mihalis; Ervens, Barbara; Tsigaridis, Kostas; Facchini, Maria Cristina

2011-08-01

This paper presents results supporting the existence of a natural source of oxalic acid over the oceans. Oxalate was detected in "clean-sector" marine aerosol samples at Mace Head (Ireland) (53°20'N, 9°54'W) during 2006, and at Amsterdam Island (37°48'S, 77°34'E) from 2003 to 2007, in concentrations ranging from 2.7 to 39 ng m-3 and from 0.31 to 17 ng m-3, respectively. The oxalate concentration showed a clear seasonal trend at both sites, with maxima in spring-summer and minima in fall-winter, being consistent with other marine biogenic aerosol components (e.g., methanesulfonic acid, non-sea-salt sulfate, and aliphatic amines). The observed oxalate was distributed along the whole aerosol size spectrum, with both a submicrometer and a supermicrometer mode, unlike the dominant submicrometer mode encountered in many polluted environments. Given its mass size distribution, the results suggest that over remote oceanic regions oxalate is produced through a combination of different formation processes. It is proposed that the cloud-mediated oxidation of gaseous glyoxal, recently detected over remote oceanic regions, may be an important source of submicrometer oxalate in the marine boundary layer. Supporting this hypothesis, satellite-retrieved glyoxal column concentrations over the two sampling sites exhibited the same seasonal concentration trend of oxalate. Furthermore, chemical box model simulations showed that the observed submicrometer oxalate concentrations were consistent with the in-cloud oxidation of typical marine air glyoxal mixing ratios, as retrieved by satellite measurements, at both sites.

Promoting effect of alkaline earth metal doping on catalytic activity of HC and NOx conversion over Pd-only three-way catalyst.

PubMed

Yang, Linyan; Lin, Siyu; Yang, Xue; Fang, Weimin; Zhou, Renxian

2014-08-30

The influence of alkaline earth metal (M=Mg, Ca, Sr and Ba) promoter on the structural/textural properties of Ce0.67Zr0.33O2 (designated as CZ) and the catalytic behavior of its supported Pd-only three-way catalyst (Pd/CZM) have been investigated. The results show that the modification with alkaline earth metal obviously improves the catalytic activity for hydrocarbon (HC) and nitrogen oxides (NOx) conversion, especially the introduction of Ba. Furthermore, the operation window of the promoted catalysts has also been widened. The doping of alkaline earth metal leads to the formation of more homogeneous Ce-Zr-M ternary solid solution with higher surface area and smaller crystallite size, and the corresponding Pd/CZM catalysts present improved reducibility of PdO species. The modification with Ca, Sr and Ba improves the thermal aging resistance, especially Ba. DRIFTS results reveal that the doping of alkaline earth metal enhances the oxygen and electron transfer ability and favors the dissociation of NO, which promotes the activation and storage capacity of the acidic atoms like NOx, and leads to enhanced catalytic activity performance. Copyright © 2014 Elsevier B.V. All rights reserved.

Two-dimensional infrared spectral signature and hydration of the oxalate dianion

PubMed Central

Kuroda, Daniel G.; Hochstrasser, Robin M.

2011-01-01

Ultrafast vibrational spectra of the aqueous oxalate ion in the region of its carboxylate asymmetric stretch modes show novel relaxation processes. Two-dimensional infrared vibrational echo spectra and the vibrational dynamics obtained from them along with measurements of the anisotropy decay provide a picture in which the localization of the oxalate vibrational excitation onto the carboxylate groups occurs in ∼450 fs. Molecular dynamics simulations are used to characterize the vibrational dynamics in terms of dihedral angle motion between the two carboxylate planes and solvation dynamics. The localization of the oxalate vibrational excitation onto the carboxylates is induced by the fluctuations in the carboxylate vibrational frequencies which are shown by theory and experiment to have a similar correlation time as the anisotropy decay. PMID:22128938

Naked-eye determination of oxalate anion in aqueous solution with copper ion and pyrocatechol violet.

PubMed

Su, Jing; Sun, Yuan-Qiang; Huo, Fang-Jun; Yang, Yu-Tao; Yin, Cai-Xia

2010-11-01

A novel strategy for the determination of oxalate anions was successfully established using a copper ion and pyrocatechol violet (PV) ensemble. The sensor ensemble can discriminate oxalate over other common anions including F(-), Cl(-), I(-), Br(-), HPO(4)(2-), PO(4)(3-), AcO(-), CO(3)(2-), SO(4)(2-), ClO(4)(-), P(2)O(7)(4-), S(2-) (deposited by Ag(+)), CN(-) (shielded by Fe(3+)) and can detect oxalate at low microgram levels in quasi-physiological aqueous solutions. The detection of the oxalate anion gives rise to a rapid observable visual color change from blue to yellow.

Characterization of metabolic network of oxalic acid biosynthesis through RNA seq data analysis of developing spikes of finger millet (Eleusine coracana): Deciphering the role of key genes involved in oxalate formation in relation to grain calcium accumulation.

PubMed

Akbar, Naved; Gupta, Supriya; Tiwari, Apoorv; Singh, K P; Kumar, Anil

2018-04-05

In the present study, we identified seven major genes of oxalic acid biosynthesis pathway (SGAT, GGAT, ICL, GLO, MHAR, APO and OXO) from developing spike transcriptome of finger millet using rice as a reference. Sequence alignment of identified genes showed high similarity with their respective homolog in rice except for OXO and GLO. Transcript abundance (FPKM) reflects the higher accumulation of identified genes in GP-1 (low calcium genotype) as compared to GP-45 (high calcium genotype) which was further confirmed by qRT-PCR analysis, indicating differential oxalate formation in both genotypes. Determination of oxalic acid and tartaric acid content in developing spikes explain that higher oxalic acid content in GP-1 however, tartaric acid content was more in GP-45. Higher calcium content in GP-45 and lower oxalate accumulation may be due to the diversion of more ascorbic acid into tartaric acid and may correspond to less formation of calcium oxalate. Our results suggest that more than one pathway for oxalic acid biosynthesis might be present in finger millet with probable predominance of ascorbate-tartarate pathway rather than glyoxalate-oxalate conversion. Thus, finger millet can be use as an excellent model system for understanding more specific role of nutrients-antinutrients interactions, as evident from the present study. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of different brewing times on soluble oxalate content of loose-packed black teas and tea bags.

PubMed

Mahdavi, Reza; Lotfi Yagin, Neda; Liebman, Michael; Nikniaz, Zeinab

2013-02-01

Because of the postulated role of increased dietary oxalate intake in calcium oxalate stone formation, the effect of different brewing times on soluble oxalate contents of loose-packed black tea and tea bags was studied. The oxalate content of 25 different samples of loose-packed black teas after brewing at 5, 10, 15, 30, and 60 min and of ten brands of tea bags after infusion for 1, 2, 3, 4, and 5 min was measured by enzymatic assay. The oxalate concentration resulting from different brewing times ranged from 4.3 to 6.2 mg/240 ml for loose-packed black teas and from 2.7 to 4.8 mg/240 ml for tea bags. There was a stepwise increase in oxalate concentration associated with increased brewing times.

Enrichment of rare earth metal ions by the highly selective adsorption of phytate intercalated layered double hydroxide.

PubMed

Jin, Cheng; Liu, Huimin; Kong, Xianggui; Yan, Hong; Lei, Xiaodong

2018-02-27

Phytate intercalated MgAl layered double hydroxide (MgAl-LDH) was prepared by an anion exchange method with the precursor NO 3 - containing MgAl-LDH. The final as-synthesized product [Mg 0.69 Al 0.31 (OH) 2 ] (phytateNa 6 ) 0.05 (NO 3 ) 0.01 ·mH 2 O (phytate-LDH) has highly selective adsorption ability for some metal ions and can be used to enrich rare earth metal ions in mixed solution, such as Pr 3+ and Ce 3+ from a mixed solution of them with Pb 2+ and Co 2+ . At first, phytate-LDH has good adsorption performance for these ions in single metal ion solutions. At low concentration (below 10 mg L -1 ), all the capture rates of the four metal ions were more than 97%, for highly toxic Pb 2+ it was even up to nearly 100%, and a high capture rate (99.87%) was maintained for Pb 2+ at a high concentration (100 mg L -1 ). When all the four metal ions are co-existing in aqueous solution, the selectivity order is Pb 2+ ≫ Pr 3+ ≈ Ce 3+ > Co 2+ . In a solution containing mixtures of the three metal ions of Pr 3+ , Ce 3+ , and Co 2+ , the selectivity order is Pr 3+ ≈ Ce 3+ ≫ Co 2+ , and in a solution containing mixtures of Pr 3+ with Co 2+ and Ce 3+ with Co 2+ , the selectivity orders are Pr 3+ ≫ Co 2+ and Ce 3+ ≫ Co 2+ , respectively. The high selectivity and adsorption capacities for Pb 2+ , Co 2+ , Pr 3+ , and Ce 3+ result in the efficient removal of Pb 2+ and enrichment of the rare earth metal ions Pr 3+ and Ce 3+ by phytate-LDH. Based on the elemental analysis, it is found that the difference of the adsorption capacities is mainly due to the different coordination number of them with phytate-LDH. With molecular simulation, we believe that the adsorption selectivity is due to the difference of the binding energy between the metal ion and phytate-LDH. Therefore, the phytate-LDH is promising for the enrichment and/or purification of the rare earth metal ions and removal of toxic metal ions from waste water.

Rare earth element and rare metal inventory of central Asia

USGS Publications Warehouse

Mihalasky, Mark J.; Tucker, Robert D.; Renaud, Karine; Verstraeten, Ingrid M.

2018-03-06

Rare earth elements (REE), with their unique physical and chemical properties, are an essential part of modern living. REE have enabled development and manufacture of high-performance materials, processes, and electronic technologies commonly used today in computing and communications, clean energy and transportation, medical treatment and health care, glass and ceramics, aerospace and defense, and metallurgy and chemical refining. Central Asia is an emerging REE and rare metals (RM) producing region. A newly compiled inventory of REE-RM-bearing mineral occurrences and delineation of areas-of-interest indicate this region may have considerable undiscovered resources.

Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals

NASA Astrophysics Data System (ADS)

Pazoki, Meysam; Jacobsson, T. Jesper; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

2016-04-01

Organic and inorganic lead halogen perovskites, and in particular, C H3N H3Pb I3 , have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, C H3N H3Ca I3,C H3N H3Sr I3 , and C H3N H3Ba I3 , as well as the reference compound, C H3N H3Pb I3 , are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of MACa I3,MASr I3 , and MABa I3 were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, C H3N H3Pb I3 , where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large

Mixed-Ligand Uranyl Polyrotaxanes Incorporating a Sulfate/Oxalate Coligand: Achieving Structural Diversity via pH-Dependent Competitive Effect.

PubMed

Xie, Zhen-Ni; Mei, Lei; Hu, Kong-Qiu; Xia, Liang-Shu; Chai, Zhi-Fang; Shi, Wei-Qun

2017-03-20

A mixed-ligand system provides an alternative route to tune the structures and properties of metal-organic compounds by introducing functional organic or inorganic coligands. In this work, five new uranyl-based polyrotaxane compounds incorporating a sulfate or oxalate coligand have been hydrothermally synthesized via a mixed-ligand method. Based on C6BPCA@CB6 (C6BPCA = 1,1'-(hexane-1,6-diyl)bis(4-(carbonyl)pyridin-1-ium), CB6 = cucurbit[6]uril) ligand, UPS1 (UO 2 (L) 0.5 (SO 4 )(H 2 O)·2H 2 O, L = C6BPCA@CB6) is formed by the alteration of initial aqueous solution pH to a higher acidity. The resulting 2D uranyl polyrotaxane sheet structure of UPS1 is based on uranyl-sulfate ribbons connected by the C6BPCA@CB6 pseudorotaxane linkers. By using oxalate ligand instead of sulfate, four oxalate-containing uranyl polyrotaxane compounds, UPO1-UPO4, have been acquired by tuning reaction pH and ligand concentration: UPO1 (UO 2 (L) 0.5 (C 2 O 4 ) 0.5 (NO 3 )·3H 2 O) in one-dimensional chain was obtained at a low pH value range (1.47-1.89) and UPO2 (UO 2 (L)(C 2 O 4 )(H 2 O)·7H 2 O)obtained at a higher pH value range (4.31-7.21). By lowering the amount of oxalate, another two uranyl polyrotaxane network UPO3 ((UO 2 ) 2 (L) 0.5 (C 2 O 4 ) 2 (H 2 O)) and UPO4 ((UO 2 ) 2 O(OH)(L) 0.5 (C 2 O 4 ) 0.5 (H 2 O)) could be acquired at a low pH value of 1.98 and a higher pH value over 6, respectively. The UPO1-UPO4 compounds, which display structural diversity via pH-dependent competitive effect of oxalate, represent the first series of mixed-ligand uranyl polyrotaxanes with organic ligand as the coligand. Moreover, the self-assembly process and its internal mechanism concerning pH-dependent competitive effect and other related factors such as concentration of the reagents and coordination behaviors of the coligands were discussed in detail.

Oxalate co-precipitation synthesis of calcium zirconate and calcium titanate powders.

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

Hernandez-Sanchez, Bernadette A.; Tuttle, Bruce Andrew

2009-06-01

Fine powders of calcium zirconate (CaZrO{sub 3}, CZ) and calcium titanate (CaTiO{sub 3}, CT) were synthesized using a nonaqueous oxalate co-precipitation route from Ca(NO{sub 3}){sub 2}{center_dot}4 H{sub 2}O and group(IV) n-butoxides (Ti(OBu{sup n}){sub 4} or Zr(OBu{sup n}){sub 4}). Several reaction conditions and batch sizes (2-35 g) were explored to determine their influence on final particle size, morphology, and phase. Characterization of the as-prepared oxalate precursors, oven dried oxalate precursors (60-90 C), and calcined powders (635-900 C) were analyzed with TGA/DTA, XRD, TEM, and SEM. Densification and sintering studies on pressed CZ pellets at 1375 and 1400 C were also performed.more » Through the developed oxalate co-precipitation route, densification temperatures for CZ were lowered by 125 C from the 1500 C firing temperature required for conventional mixed oxide powders. Low field electrical tests of the CZ pellets indicated excellent dielectric properties with dielectric constants of {approx}30 and a dissipation factor of 0.0004 were measured at 1 kHz.« less

Molecule-based magnets formed by bimetallic three-dimensional oxalate networks and chiral tris(bipyridyl) complex cations. The series [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = oxalate dianion).

PubMed

Coronado, E; Galán-Mascarós, J R; Gómez-García, C J; Martínez-Agudo, J M

2001-01-01

The synthesis, structure, and physical properties of the series of molecular magnets formulated as [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = oxalate dianion) are presented. All the compounds are isostructural to the [Ru(bpy)3][ClO4][MnCr(ox)3] member whose structure (cubic space group P4(1)32 with a = 15.506(2) A, Z = 4) consists of a three-dimensional bimetallic network formed by alternating MII and CrIII ions connected by oxalate anions. The identical chirality (lambda in the solved crystal) of all the metallic centers determines the 3D chiral structure adopted by these compounds. The anionic 3D sublattice leaves some holes where the chiral [Z(bpy)3]2+ and ClO4- counterions are located. These compounds behave as soft ferromagnets with ordering temperatures up to 6.6 K and coercive fields up to 8 mT.

Study on the Key Technology of High Purity Strontium Titanate Powder Synthesized from Oxalic Acid Co-sediment Precipitation

NASA Astrophysics Data System (ADS)

Bi, Xiaoguo; Dong, Yingnan; Li, Yingjie; Niu, Wei; Tang, Jian; Ding, Shuang; Li, Meiyang

2017-09-01

Oxalate coprecipitation is applied in this paper, high purity titanium tetrachloride, and after the purification of strontium chloride, match with a certain concentration of solution, oxalate and strontium chloride and titanium tetrachloride in 1.005:1.000 make strontium titanium mixture ratio, slowly under 60°C to join in oxalic acid solution, aging around 4 h, get oxygen titanium strontium oxalate (SrTiO(C2O4)2 • 4H2 ) precipitation, after washing, drying and other process made oxygen titanium strontium oxalate powder.

[Quantitative mineralogical analyzes of kidney stones and diagnosing metabolic disorders in female patients with calcium oxalate urolithiasis].

PubMed

Kustov, A V; Moryganov, M A; Strel'nikov, A I; Zhuravleva, N I; Airapetyan, A O

2016-02-01

To conduct a complex examination of female patients with calcium oxalate urolithiasis to detect metabolic disorders, leading to stone formation. The study was carried out using complex physical and chemical methods, including quantitative X-ray phase analysis of urinary stones, pH measurement, volumetry, urine and blood spectrophotometry. Quantitative mineralogical composition of stones, daily urine pH profile, daily urinary excretion of ions of calcium, magnesium, oxalate, phosphate, citrate and uric acid were determined in 20 female patients with calcium oxalate stones. We have shown that most of the stones comprised calcium oxalate monohydrate or mixtures of calcium oxalate dihydrate and hydroxyapatite. Among the identified abnormalities, the most frequent were hypocitraturia and hypercalciuria - 90 and 45%, respectively. Our findings revealed that the daily secretion of citrate and oxalate in patients older than 50 years was significantly lower than in younger patients. In conclusion, daily urinary citrate excretion should be measured in female patients with calcium oxalate stones. This is necessary both to determine the causes of stone formation, and to monitor the effectiveness of citrate therapy.

Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

PubMed

Gagné, Olivier Charles; Hawthorne, Frank Christopher

2016-08-01

Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in

Intercomparison of the measurements of oxalic acid in aerosols by gas chromatography and ion chromatography

NASA Astrophysics Data System (ADS)

Kawamura, Kimitaka; Barrie, Leonard A.; Toom-Sauntry, Desiree

2010-12-01

Oxalate, the anion of oxalic acid, is one of the most abundant measurable organic species in atmospheric aerosols. Traditionally, this bifunctional species has been measured by gas chromatography (GC) after derivatization to butyl ester and by ion chromatography (IC) without derivatization. However, there are few published comparisons of the two techniques. Here, we report the results of an intercomparison study for the measurement of oxalic acid in Arctic aerosols (<2.5 μm, n = 82) collected in 1992 using GC and IC. The concentrations of oxalic acid by GC ranged from 6.5-59.1 ng m -3 (av. 26.0 ng m -3, median 26.2 ng m -3) whereas those by IC ranged from 6.6-52.1 ng m -3 (av. 26.6 ng m -3, median 25.4 ng m -3). They showed a good correlation ( r = 0.84) with a slope of 0.96. Thus, observations of oxalate obtained by GC employing dibutyl esters are almost equal to those by IC. Because the accuracy of oxalic acid by GC method largely depends on the method used, it is important to strictly examine the recovery in each study.

First examples of ternary lanthanide 5-aminoisophthalate complexes: Hydrothermal syntheses and structures of lanthanide coordination polymers with 5-aminoisophthalate and oxalate

NASA Astrophysics Data System (ADS)

Liu, Chong-Bo; Wen, Hui-Liang; Tan, Sheng-Shui; Yi, Xiu-Guang

2008-05-01

Two new lanthanide coordination polymers with mixed-carboxylates, [Ln(OX)(HAPA)(H 2O)] n[Ln = Eu ( 1), Ho ( 2); H 2APA = 5-aminoisophthalic acid; OX = oxalate] were obtained by hydrothermal reactions, and characterized by single crystal X-ray diffraction, elemental analysis and IR spectra. Complexes 1 and 2 are both 3-D supramolecular structure, in which lanthanide ions are bridged by oxalate and 5-aminoisophthalate ligands forming 2-D metal-organic framework, and 2-D networks are further architectured to form 3-D supramolecular structures by hydrogen bonds. The two carboxylate groups of H 2APA ligand are all deprotonated and exhibit chelating and bridging bidentate coordination modes, respectively, and the amino group in HAPA presents - NH3+ in the titled complexes. The thermogravimetric analysis was carried out to examine the thermal stability of the titled complexes. And the photoluminescence property of 1 was investigated.

Hydrometallurgical separation of rare earth elements, cobalt and nickel from spent nickel-metal-hydride batteries

NASA Astrophysics Data System (ADS)

Rodrigues, Luiz Eduardo Oliveira Carmo; Mansur, Marcelo Borges

The separation of rare earth elements, cobalt and nickel from NiMH battery residues is evaluated in this paper. Analysis of the internal content of the NiMH batteries shows that nickel is the main metal present in the residue (around 50% in weight), as well as potassium (2.2-10.9%), cobalt (5.1-5.5%), rare earth elements (15.3-29.0%) and cadmium (2.8%). The presence of cadmium reveals that some Ni-Cd batteries are possibly labeled as NiMH ones. The leaching of nickel and cobalt from the NiMH battery powder with sulfuric acid is efficient; operating variables temperature and concentration of H 2O 2 has no significant effect for the conditions studied. A mixture of rare earth elements is separated by precipitation with NaOH. Finally, solvent extraction with D2EHPA (di-2-ethylhexyl phosphoric acid) followed by Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) can separate cadmium, cobalt and nickel from the leach liquor. The effect of the main operating variables of both leaching and solvent extraction steps are discussed aiming to maximize metal separation for recycling purposes.

Heterogeneous Delivery of Silicate and Metal to the Earth via Large Planetesimals

NASA Astrophysics Data System (ADS)

Marchi, S.; Canup, R. M.; Walker, R. J.

2017-12-01

Earth's mantle abundances of at least some highly siderophile elements, (HSE; Re, Os, Ir, Ru, Pt, Rh, Pd, and Au), are much higher than would result from metal-silicate equilibration during terrestrial core formation, and can be better explained as a result of late accretion of a minimum of 0.5% Earth's masses after core formation was complete. Traditional models assume that HSEs delivered by late projectiles completely mixed and chemically equilibrated with the Earth's mantle. This appears likely for undifferentiated, well-mixed projectiles, or for relatively small, differentiated projectiles. However several arguments suggest that late projectiles may have been large (> 1500 km in diameter) and differentiated, and in this case, portions of the projectile's core may merge with the Earth's core, rather than being mixed into the Earth's mantle. We investigate projectile mixing with a suite of SPH simulations of differentiated planetesimal colliding with the Earth. A range of outcomes emerge from our simulations suggesting that for large impactors (>1500 km), the delivery of HSE to the Earth's mantle may be disproportionate with the overall delivery of mass. For impacts with impact angles < 45° , between ˜ 20% to 80% of the impactor's core may merge directly with the Earth's core; while for impact angle > 60°, most of the impactor core escapes for moderate impact speeds. An implication is that the late accreted mass inferred from terrestrial HSE abundances may be a substantial underestimate, by a factor 2-5. In addition, partial mixing of projectiles result in an enrichment in mantle vs core material delivered to the bulk silicate Earth, implying substantial compositional variations in the accreted mass. Such variations could produce initially localized domains in Earth's mantle with distinct, mass independent isotopic signatures, given the isotopic variability resulting from nucleosynthetic heterogeneities among genetically diverse meteorites. In general we find

Improving the two-step remediation process for CCA-treated wood. Part I, Evaluating oxalic acid extraction

Treesearch

Carol Clausen

2004-01-01

In this study, three possible improvements to a remediation process for chromated-copper-arsenate (CCA) treated wood were evaluated. The process involves two steps: oxalic acid extraction of wood fiber followed by bacterial culture with Bacillus licheniformis CC01. The three potential improvements to the oxalic acid extraction step were (1) reusing oxalic acid for...

The Relationship between Serum Oxalic Acid, Central Hemodynamic Parameters and Colonization by Oxalobacter formigenes in Hemodialysis Patients.

PubMed

Gulhan, Baris; Turkmen, Kultigin; Aydin, Merve; Gunay, Murat; Cıkman, Aytekin; Kara, Murat

2015-06-01

Elevated pulse wave velocity (PWV) and central aortic blood pressures are independent predictors of increased cardiovascular morbidity and mortality in hemodialysis (HD) patients. Oxalic acid is a uremic retention molecule that is extensively studied in the pathogenesis of calcium oxalate stones. Oxalobacter formigenes, a member of the colon microbiota, has important roles in oxalate homeostasis. Data regarding the colonization by and the exact role of O. formigenes in the pathogenesis of oxalic acid metabolism in HD patients are scant. Hence, we aimed to determine the relationship between fecal O. formigenes colonization, serum oxalic acid and hemodynamic parameters in HD patients with regard to the colo-reno-cardiac axis. Fifty HD patients were enrolled in this study. PWV and central aortic systolic (cASBP) and diastolic blood pressures (cADBP) were measured with a Mobil-O-Graph (I.E.M. GmbH, Stolberg, Germany). Serum oxalic acid levels were assessed by ELISA, and fecal O. formigenes DNA levels were isolated and measured by real-time PCR. Isolation of fecal O. formigenes was found in only 2 HD patients. One of them had 113,609 copies/ml, the other one had 1,056 copies/ml. Serum oxalic acid levels were found to be positively correlated with PWV (r = 0.29, p = 0.03), cASBP (r = 0.33, p = 0.001) and cADBP (r = 0.42, p = 0.002) and negatively correlated with LDL (r = -0.30, p = 0.03). In multivariate linear regression analysis, PWV was independently predicted by oxalic acid, glucose and triglyceride. This is the first study that demonstrates the absence of O. formigenes as well as a relation between serum oxalic acid and cASBP, cADBP and PWV in HD patients. Replacement of O. formigenes with pre- and probiotics might decrease serum oxalic acid levels and improve cardiovascular outcomes in HD patients.

The genetic composition of Oxalobacter formigenes and its relationship to colonization and calcium oxalate stone disease

PubMed Central

Knight, John; Deora, Rajendar; Assimos, Dean G.; Holmes, Ross P.

2013-01-01

Oxalobacter formigenes is a unique intestinal organism that relies on oxalate degradation to meet most of its energy and carbon needs. A lack of colonization is a risk factor for calcium oxalate stone disease. Protection against calcium oxalate stone disease appears to be due to the oxalate degradation that occurs in the gut on low calcium diets with a possible further contribution from intestinal oxalate secretion. Much remains to be learned about how the organism establishes and maintains gut colonization and the precise mechanisms by which it modifies stone risk. The sequencing and annotation of the genomes of a Group 1 and a Group 2 strain of O. formigenes should provide the informatic tools required for the identification of the genes and pathways associated with colonization and survival. In this review we have identified genes that may be involved and where appropriate suggested how they may be important in calcium oxalate stone disease. Elaborating the functional roles of these genes should accelerate our understanding of the organism and clarify its role in preventing stone formation. PMID:23632911

Computational study on nitronium and nitrosonium oxalate: potential oxidizers for solid rocket propulsion?

PubMed

Gökçinar, Elif; Klapötke, Thomas M; Kramer, Michael P

2010-08-26

The enthalpies of formation for solid ionic nitrosonium oxalate, [NO](2)[O(2)C-CO(2)], nitronium oxalate, [NO(2)](2)[O(2)C-CO(2)], as well as covalent bis(nitroso)oxalic acid, ON-O(2)C-CO(2)-NO, and oxalic acid dinitrate ester, O(2)N-O(2)C-CO(2)-NO(2), were calculated using the complete basis set (CBS-4M) method of Petersson and coworkers to obtain very accurate energies. For the nitrosonium species, the ionic form ([NO](2)[O(2)C-CO(2)]) was identified as the more stable isomer, whereas for the nitrosonium compound, the covalently bound dinitrate ester (O(2)N-O(2)C-CO(2)-NO(2)) was found to be more stable. The combustion parameters with respect to possible use as ingredients in solid rocket motors for both stable species were calculated using the EXPLO5 and the ICT code. The performance of an aluminized formulation with covalently bound dinitrate ester (O(2)N-O(2)C-CO(2)-NO(2)) was shown to be comparable to that of ammonium perchlorate/aluminum. This makes oxalic acid dinitrate ester a potentially interesting perchlorate-free and environmentally benign oxidizer for solid rocket propulsion.

Effect of calcium oxalate on the photocatalytic degradation of Orange II on ZnO surface

NASA Astrophysics Data System (ADS)

Bassaid, S.; Ziane, B.; Badaoui, M.; Chaib, M.; Robert, D.

2013-06-01

The photocatalytic degradation of aqueous solution of Orange II, has been investigated in the presence of ZnO catalyst with calcium oxalate as sacrificial agent. This study demonstrated that the performance of ZnO photocatalyst can be improved by addition of calcium oxalate. Results show that adsorption is an important parameter controlling the degradation phenomena. Indeed, the added oxalate causes a drop in the pH medium, what causes a better adsorption of Orange II on the ZnO surface. The effect of calcium oxalate is to increase the concentration of superoxides (O{2/·-}) and hydroperoxides (HO2·) radicals, which are key intermediaries in the mechanism of photodegradation because of their powerful force of oxidation.

Equilibrium aluminium hydroxo-oxalate phases during initial clay formation; H +-Al 3+-oxalic acid-Na + system

NASA Astrophysics Data System (ADS)

Bilinski, Halka; Horvath, Laszlo; Ingri, Nils; Sjöberg, Staffan

1986-09-01

The conditions necessary for initial clay formation have been studied in different model systems comprising different organic acids besides Si and Al. In the present paper the solid phases and the precipitation boundary characterizing the subsystem H +-Al 3+-oxalic acid (H 2L) are discussed. pH and tyndallometric measurements were performed in an ionic medium of 0.6 M Na(Cl) at 25 °C. The two phases Al 3(OH) 7(C 2O 4) · 3H 2O (phase I) and NaAl(OH) 2(C 2O 4) · 3H 2O (phase II) determine the precipitation boundary. The following formation constants for the two phases were deduced: lgβ1 = lg([ Al3+] -3[ H2C2O4] -1[ H+] 9 = -21.87 ± 0.08 and lgβ11 = lg([ Al3+] -1[ H2C2O4] -1[ H+] 4 = -5.61 ± 0.06. Phase I exists in the range [ Al] tot≥ 10 -4.4moldm-3,[ H2C2O4] tot ≥ 10 -4.9moldm-3 and at pH < 6.8, thus being a possible precipitate in oxalic-rich natural waters. The more soluble sodium phase is unlikely to exist in natural waters. The two phases are metastable relative to crystalline gibbsite and may be considered as the first precipitation step in the transition from aqueous Al oxalates down to stable Al hydroxide. Model calculations illustrating these competing hydrolysis-complexation reactions are discussed in terms of predominance and speciation diagrams. The solid phases have been characterized by X-ray analysis of powders, TGA and IR spectra, and tentative structures are proposed. Phase I seems to be an octahedral layer structure, in which 3/5 of the octahedral sites between two close packed oxygen sheets are occupied by Al 3+ and the oxalate ion acts as a bridge ligand between two aluminium atoms. Phase II forms a more open sheet structure and has ion exchange properties. Powder data for a phase crystallized from the studied solution after a year are also presented. This phase, Na 4Al 2(OH) 2(C 2O 4) 4 · 10H 2O, supports the results from the equilibrium analysis of recent solution data by SJöBERG and ÖHMAN (1985), who have found the dinuclear

Kinetics of the mechanochemical synthesis of alkaline-earth metal amides

NASA Astrophysics Data System (ADS)

Garroni, Sebastiano; Takacs, Laszlo; Leng, Haiyan; Delogu, Francesco

2014-07-01

A phenomenological framework is developed to model the kinetics of the formation of alkaline-earth metal amides by the ball milling induced reaction of their hydrides with gaseous ammonia. It is shown that the exponential character of the kinetic curves is modulated by the increase of the total volume of the powder inside the reactor due to the substantially larger molar volume of the products compared to the reactants. It is claimed that the volume of powder effectively processed during each collision connects the transformation rate to the physical and chemical processes underlying the mechanochemical transformations.

Tunable optical properties of some rare earth elements-doped mayenite Ca12Al14O33 nanopowders elaborated by oxalate precursor route

NASA Astrophysics Data System (ADS)

Rashad, Mohamed M.; Mostafa, Ahmed G.; Mwakikunga, Bonex W.; Rayan, Diaa A.

2017-01-01

Rare earth (RE) ions-doped mayenite Ca12Al14- x RE x O33 nanopowders (where RE = La and Gd and x = 0-1.0) were synthesized using the oxalate precursor technique. The as-prepared precursors were calcined at 800 °C for 2 h. Obviously, all RE-doped Ca12Al14- x RE x O33 possessed a well-crystalline cubic mayenite phase till RE content of 0.8. The crystallo-chemical aspects including crystallite size, lattice parameters, theoretical X-ray density and bulk density were robustly on RE nature and ratio. The microstructure and the average grain size were significantly influenced by the RE kind and content. The high transparency of Ca12Al14- x RE x O33 over 80% was found to be evinced in the visible wavelength range of 400-800 nm. Besides, the incorporation of RE cation minimized the direct band gap energy from 4.42 eV for pure mayenite to 3.85 and 3.59 eV with x value 1.0 of La3+ and Gd3+ ions. The photoluminescence spectra of pure mayenite nanoparticles showed that the band edge emission ( λ exc = 248 nm) with an intense visible emission band at 360 nm was detected. Otherwise, the band edge emission showed a slight shift toward short wavelength due to the substitution Al3+ by RE3+ ions. Such results open a new avenue for application of mayenite as a good candidate for transparent low-temperature electron conductor for optoelectronics applications.

An Oxalyl-CoA Synthetase Is Involved in Oxalate Degradation and Aluminum Tolerance1[OPEN

PubMed Central

Fan, Wei; Xu, Jia Meng; Gong, Yu Long; Jin, Jian Feng; Chen, Wei Wei; Liu, Ling Yu; Hai, Mei Rong

2016-01-01

Acyl Activating Enzyme3 (AAE3) was identified to be involved in the catabolism of oxalate, which is critical for seed development and defense against fungal pathogens. However, the role of AAE3 protein in abiotic stress responses is unknown. Here, we investigated the role of rice bean (Vigna umbellata) VuAAE3 in Al tolerance. Recombinant VuAAE3 protein has specific activity against oxalate, with Km = 121 ± 8.2 µm and Vmax of 7.7 ± 0.88 µmol min−1 mg−1 protein, indicating it functions as an oxalyl-CoA synthetase. VuAAE3-GFP localization suggested that this enzyme is a soluble protein with no specific subcellular localization. Quantitative reverse transcription-PCR and VuAAE3 promoter-GUS reporter analysis showed that the expression induction of VuAAE3 is mainly confined to rice bean root tips. Accumulation of oxalate was induced rapidly by Al stress in rice bean root tips, and exogenous application of oxalate resulted in the inhibition of root elongation and VuAAE3 expression induction, suggesting that oxalate accumulation is involved in Al-induced root growth inhibition. Furthermore, overexpression of VuAAE3 in tobacco (Nicotiana tabacum) resulted in the increase of Al tolerance, which was associated with the decrease of oxalate accumulation. In addition, NtMATE and NtALS3 expression showed no difference between transgenic lines and wild-type plants. Taken together, our results suggest that VuAAE3-dependent turnover of oxalate plays a critical role in Al tolerance mechanisms. PMID:27650448

Isolation and characterization of mesophilic, oxalate-degrading Streptomyces from plant rhizosphere and forest soils

NASA Astrophysics Data System (ADS)

Sahin, Nurettin

2004-10-01

The present work was aimed at the isolation of additional new pure cultures of oxalate-degrading Streptomyces and its preliminary characterization for further work in the field of oxalate metabolism and taxonomic studies. Mesophilic, oxalate-degrading Streptomyces were enriched and isolated from plant rhizosphere and forest soil samples. Strains were examined for cultural, morphological (spore chain morphology, spore mass colour, diffusible and melanin pigment production), physiological (antibiosis, growth in the presence of inhibitory compounds, assimilation of organic acids and enzyme substrates) and chemotaxonomic characters (cellular lipid components and diagnostic cell-wall diamino acid). The taxonomic data obtained were analysed by using the simple matching (SSM) and Jaccard (SJ) coefficients, clustering was achieved using the UPGMA algorithm. All strains were able to utilize sodium-, potassium-, calcium- and ammonium-oxalate salts. Based on the results of numerical taxonomy, isolates were grouped into five cluster groups with a ≥70% SSM similarity level. Streptomyces rochei was the most common of the cluster groups, with a Willcox probability of P>0.8. Streptomyces antibioticus, S. anulatus, S. fulvissimus, S. halstedii and S. violaceusniger are newly reported as oxalate-utilizing Streptomyces.

The role of intestinal oxalate transport in hyperoxaluria and the formation of kidney stones in animals and man

PubMed Central

Whittamore, Jonathan M.; Hatch, Marguerite

2016-01-01

The intestine exerts a considerable influence over urinary oxalate in two ways, through the absorption of dietary oxalate and by serving as an adaptive extra-renal pathway for elimination of this waste metabolite. Knowledge of the mechanisms responsible for oxalate absorption and secretion by the intestine therefore have significant implications for understanding the etiology of hyperoxaluria, as well as offering potential targets for future treatment strategies for calcium oxalate kidney stone disease. In this review, we present the recent developments and advances in this area over the past 10 years, and put to the test some of the new ideas that have emerged during this time, using human and mouse models. A key focus for our discussion are the membrane-bound anion exchangers, belonging to the SLC26 gene family, some of which have been shown to participate in transcellular oxalate absorption and secretion. This has offered the opportunity to not only examine the roles of these specific transporters, revealing their importance to oxalate homeostasis, but to also probe the relative contributions made by the active transcellular and passive paracellular components of oxalate transport across the intestine. We also discuss some of the various physiological stimuli and signaling pathways which have been suggested to participate in the adaptation and regulation of intestinal oxalate transport. Finally, we offer an update on research into Oxalobacter formigenes, alongside recent investigations of other oxalate-degrading gut bacteria, in both laboratory animals and humans. PMID:27913853

An oxalyl-CoA synthetase is important for oxalate metabolism in Saccharomyces cerevisiae

USDA-ARS?s Scientific Manuscript database

Although oxalic acid is common in nature, our understanding of the mechanism(s) regulating its turnover remains incomplete. In this study we identify Saccharomyces cerevisiae acyl-activating enzyme 3 (ScAAE3) as an enzyme capable of catalyzing the conversion of oxalate to oxalyl-CoA. Based on our fi...

Diminution of oxalate induced renal tubular epithelial cell injury and inhibition of calcium oxalate crystallization in vitro by aqueous extract of Tribulus terrestris.

PubMed

Aggarwal, A; Tandon, S; Singla, S K; Tandon, C

2010-01-01

Recurrence and persistent side effects of present day treatment for urolithiasis restrict their use, so an alternate solution, using phytotherapy is being sought. The present study attempted to evaluate the antilithiatic properties of Tribulus terrestris commonly called as "gokhru" which is often used in ayurveda to treat various urinary diseases including urolithiasis. The activity of Tribulus terrestris was investigated on nucleation and the growth of the calcium oxalate (CaOx) crystals as well as on oxalate induced cell injury of NRK 52E renal epithelial cells. Tribulus terrestris extract exhibited a concentration dependent inhibition of nucleation and the growth of CaOx crystals. When NRK-52E cells were injured by exposure to oxalate for 72 h, Tribulus terrestris extract prevented the injury in a dose-dependent manner. On treatment with the different concentrations of the plant, the cell viability increased and lactate dehydrogenase release decreased in a concentration dependent manner. The current data suggests that Tribulus terrestris extract not only has a potential to inhibit nucleation and the growth of the CaOx crystals but also has a cytoprotective role. Our results indicate that it could be a potential candidate for phytotherapy against urolithiasis.

Dehydrogenation of secondary amines: synthesis, and characterization of rare-earth metal complexes incorporating imino- or amido-functionalized pyrrolyl ligands.

PubMed

Li, Qinghai; Zhou, Shuangliu; Wang, Shaowu; Zhu, Xiancui; Zhang, Lijun; Feng, Zhijun; Guo, Liping; Wang, Fenhua; Wei, Yun

2013-02-28

The dehydrogenation of pyrrolyl-functionalized secondary amines initiated by rare-earth metal amides was systematically studied. Reactions of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with pyrrolyl-functionalized secondary amines 2-(t)BuNHCH(2)-5-R-C(4)H(2)NH (R = H (1), R = (t)Bu (2)) led to dehydrogenation of the secondary amines with isolation of imino-functionalized pyrrolyl rare-earth metal complexes [2-(t)BuN=CH-5-R-C(4)H(2)N](2)REN(SiMe(3))(2) (R = H, RE = Y (3a), Dy (3b), Yb (3c), Eu (3d); R = (t)Bu, RE = Y (4a), Dy (4b), Er (4c)). The mixed ligands erbium complex [2-(t)BuNCH(2)-5-(t)Bu-C(4)H(2)N]Er[2-(t)BuN=CH-5-(t)BuC(4)H(2)N](2)ClLi(2)(THF) (4c') was isolated in a short reaction time for the synthesis of complex 4c. Reaction of the deuterated pyrrolyl-functionalized secondary amine 2-((t)BuNHCHD)C(4)H(3)NH with yttrium amide [(Me(3)Si)(2)N](3)Y(μ-Cl)Li(THF)(3) further proved that pyrrolyl-amino ligands were transferred to pyrrolyl-imino ligands. Treatment of 2-((t)BuNHCH(2))C(4)H(3)NH (1) with excess (Me(3)Si)(2)NLi gave the only pyrrole deprotonated product {[η(5):η(2):η(1)-2-((t)BuNHCH(2))C(4)H(3)N]Li(2)N(SiMe(3))(2)}(2) (5), indicating that LiN(SiMe(3))(2) could not dehydrogenate the secondary amines to imines and rare-earth metal ions had a decisive effect on the dehydrogenation. The reaction of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with 1 equiv. of more bulky pyrrolyl-functionalized secondary amine 2-[(2,6-(i)Pr(2)C(6)H(3))NHCH(2)](C(4)H(3)NH) (6) in toluene afforded the only amine and pyrrole deprotonated dinuclear rare-earth metal amido complexes {(μ-η(5):η(1)):η(1)-2-[(2,6-(i)Pr(2)C(6)H(3))NCH(2)]C(4)H(3)N]LnN(SiMe(3))(2)}(2) (RE = Nd (7a), Sm (7b), Er (7c)), no dehydrogenation of secondary amine to imine products were observed. On the basis of experimental results, a plausible mechanism for the dehydrogenation of secondary amines to imines was proposed.

Extraction of trivalent rare-earth metal nitrates by solutions of tributyl phosphate and diisooctylmethylphosphonate in kerosene

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

Pyartman, A.K.; Puzikov, E.A.; Kopyrin, A.A.

1995-01-01

Isotherms of extraction of trivalent rare-earth metal nitrates in the series lanthanum-lutetium, yttrium by 0.5-2.5 M solutions of tri-n-buty1 phosphate and diisooctyl methylphosphonate in kerosene at 298.15 K, pH 2 are presented. The influence of the ionic strength of aqueous phase and extractant concentration on the concentration extraction constants in the case of formation of metal(III) trisolvates in organic phase is given by equation.

Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

PubMed

De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

2014-03-28

New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

Rapid microwave-assisted acid extraction of southern pine waste wood to remove metals from chromated copper arsenate (CCA) treatment

Treesearch

Chung-Yun Hse; Todd F. Shupe; Bin Yu

2013-01-01

Recovery of metals from chromated copper arsenate (CCA)-treated southern pine wood particles was investigated by extraction in a microwave reactor with binary combinations of acetic acid (AA), oxalic acid (OxA), and phosphoric acid (PhA). Use of OxA was not successful, as insoluble copper oxalate complexes impeded copper removal. The combination of OxA and AA also had...

The Relationship between Serum Oxalic Acid, Central Hemodynamic Parameters and Colonization by Oxalobacter formigenes in Hemodialysis Patients

PubMed Central

Gulhan, Baris; Turkmen, Kultigin; Aydin, Merve; Gunay, Murat; Cıkman, Aytekin; Kara, Murat

2015-01-01

Background/Objective Elevated pulse wave velocity (PWV) and central aortic blood pressures are independent predictors of increased cardiovascular morbidity and mortality in hemodialysis (HD) patients. Oxalic acid is a uremic retention molecule that is extensively studied in the pathogenesis of calcium oxalate stones. Oxalobacter formigenes, a member of the colon microbiota, has important roles in oxalate homeostasis. Data regarding the colonization by and the exact role of O. formigenes in the pathogenesis of oxalic acid metabolism in HD patients are scant. Hence, we aimed to determine the relationship between fecal O. formigenes colonization, serum oxalic acid and hemodynamic parameters in HD patients with regard to the colo-reno-cardiac axis. Methods Fifty HD patients were enrolled in this study. PWV and central aortic systolic (cASBP) and diastolic blood pressures (cADBP) were measured with a Mobil-O-Graph (I.E.M. GmbH, Stolberg, Germany). Serum oxalic acid levels were assessed by ELISA, and fecal O. formigenes DNA levels were isolated and measured by real-time PCR. Results Isolation of fecal O. formigenes was found in only 2 HD patients. One of them had 113,609 copies/ml, the other one had 1,056 copies/ml. Serum oxalic acid levels were found to be positively correlated with PWV (r = 0.29, p = 0.03), cASBP (r = 0.33, p = 0.001) and cADBP (r = 0.42, p = 0.002) and negatively correlated with LDL (r = −0.30, p = 0.03). In multivariate linear regression analysis, PWV was independently predicted by oxalic acid, glucose and triglyceride. Conclusions This is the first study that demonstrates the absence of O. formigenes as well as a relation between serum oxalic acid and cASBP, cADBP and PWV in HD patients. Replacement of O. formigenes with pre- and probiotics might decrease serum oxalic acid levels and improve cardiovascular outcomes in HD patients. PMID:26195968

Extraction of U(VI) from oxalate solutions using tetradecylammonium oxalate (in Russian)

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

Kuzina, M.G.; Lipovskii, A.A.

1973-07-01

The extraction of U(VI) from oxalate solutions at various pH values was studied. It was shown that, as a function of the extractant and uranium concentration ratios, the latter was extracted in the form of different acido and hydroxyacido complexes. With excess extractant, the compounds were (R/sub 4/N)/ sub 2/UO/sub 2/Ox/sub 2/ at lo w pH values of the aqueous solution and (R/sub 4/ N)/sub 2/UO/sub 2/Ox(OH)/sub 2/ at h igh values. When there was a deficit of the extractant, different hydroxyacido complexes were formed. (tr-auth)

Effect of vitamin C supplements on urinary oxalate and pH in calcium stone-forming patients.

PubMed

Baxmann, Alessandra Calábria; De O G Mendonça, Claudia; Heilberg, Ita Pfeferman

2003-03-01

The contribution of ascorbate to urinary oxalate is controversial. The present study aimed to determine whether urinary oxalate and pH may be affected by vitamin C supplementation in calcium stone-forming patients. Forty-seven adult calcium stone-forming patients received either 1 g (N=23) or 2 g (N=24) of vitamin C supplement for 3 days and 20 healthy subjects received 1 g. A 24-hour urine sample was obtained both before and after vitamin C for calcium, oxalate, magnesium, citrate, sodium, potassium, and creatinine determination. The Tiselius index was used as a calcium oxalate crystallization index. A spot fasting morning urine sample was also obtained to determine the urinary pH before and after vitamin C. Fasting urinary pH did not change after 1 g (5.8 +/- 0.6 vs. 5.8 +/- 0.7) or 2 g vitamin C (5.8 +/- 0.8 vs. 5.8 +/- 0.7). A significant increase in mean urinary oxalate was observed in calcium stone-forming patients receiving either 1 g (50 +/- 16 vs. 31 +/- 12 mg/24 hours) or 2 g (48 +/- 21 vs. 34 +/- 12 mg/24 hours) of vitamin C and in healthy subjects (25 +/- 12 vs. 39 +/- 13 mg/24 hours). A significant increase in mean Tiselius index was observed in calcium stone-forming patients after 1 g (1.43 +/- 0.70 vs. 0.92 +/- 0.65) or 2 g vitamin C (1.61 +/- 1.05 vs. 0.99 +/- 0.55) and in healthy subjects (1.50 +/- 0.69 vs. 0.91 +/- 0.46). Ancillary analyses of spot urine obtained after vitamin C were performed in 15 control subjects in vessels with or without ethylenediaminetetraacetic acid (EDTA) with no difference in urinary oxalate between them (28 +/- 23 vs. 26 +/- 21 mg/L), suggesting that the in vitro conversion of ascorbate to oxalate did not occur. These data suggest that vitamin C supplementation may increase urinary oxalate excretion and the risk of calcium oxalate crystallization in calcium stone-forming patients.

The adsorption kinetics of metal ions onto different microalgae and siliceous earth.

PubMed

Schmitt, D; Müller, A; Csögör, Z; Frimmel, F H; Posten, C

2001-03-01

In the present work the adsorption kinetics of the six metal ions aluminum, zinc, mercury, lead, copper, and cadmium onto living microalgae were measured. The freshwater green microalga Scenedesmus subspicatus, the brackish water diatom Cyclotella cryptica, the seawater diatom Phaeodactylum tricornutum, and the seawater red alga Porphyridium purpureum were the subject of investigation. In most cases the adsorption rate of the metals could be well described by using the equation of the Langmuir adsorption rate expression. Inverse parameter estimation allowed the determination of the rate constants of the adsorption process and the maximum metal content of the algae. The highest values for the rate constant were obtained for Porphyridium purpureum followed by Phaeodactylum tricornutum. High values for the maximum content were obtained for Cyclotella cryptica and Scenedesmus subspicatus. The maximum rate constant was 24.21 h-1 for the adsorption of Hg to Porphyridium purpureum whereas the maximum metal content (0.243 g g-1) was obtained for Zn on Cyclotella cryptica. A comparison of these values with those obtained for the mineral siliceous earth exhibiting low maximum content and high adsorption rates reveals that the mechanism of adsorption onto the algae is a mixture of adsorption and accumulation.

The oxalic acid biosynthetic activity of Burkholderia mallei is encoded by a single locus

USDA-ARS?s Scientific Manuscript database

Although it is known that oxalic acid provides a selective advantage to the secreting microbe, our understanding of how this acid is biosynthesized remains incomplete. This study reports the identification, cloning, and partial characterization of the oxalic acid biosynthetic enzyme from the animal ...

A volatile topic: Parsing out the details of Earth's formation through experimental metal-silicate partitioning of volatile and moderately volatile elements

NASA Astrophysics Data System (ADS)

Mahan, B. M.; Siebert, J.; Blanchard, I.; Badro, J.; Sossi, P.; Moynier, F.

2017-12-01

Volatile and moderately volatile elements display different volatilities and siderophilities, as well as varying sensitivity to thermodynamic controls (X, P, T, fO2) during metal-silicate differentiation. The experimental determination of the metal-silicate partitioning of these elements permits us to evaluate processes controlling the distribution of these elements in Earth. In this work, we have combined metal-silicate partitioning data and results for S, Sn, Zn and Cu, and input these characterizations into Earth formation models. Model parameters such as source material, timing of volatile delivery, fO2 path, and degree of impactor equilibration were varied to encompass an array of possible formation scenarios. These models were then assessed to discern plausible sets of conditions that can produce current observed element-to-element ratios (e.g. S/Zn) in the Earth's present-day mantle, while also satisfying current estimates on the S content of the core, at no more than 2 wt%. The results of our models indicate two modes of accretion that can maintain chondritic element-to-element ratios for the bulk Earth and can arrive at present-day mantle abundances of these elements. The first mode requires the late addition of Earth's entire inventory of these elements (assuming a CI-chondritic composition) and late-stage accretion that is marked by partial equilibration of large impactors. The second, possibly more intuitive mode, requires that Earth accreted - at least initially - from volatile poor material preferentially depleted in S relative to Sn, Zn, and Cu. From a chemical standpoint, this source material is most similar to type I chondrule rich (and S poor) materials (Hewins and Herzberg, 1996; Mahan et al., 2017; Amsellem et al., 2017), such as the metal-bearing carbonaceous chondrites.

Metal oxide films on metal

DOEpatents

Wu, Xin D.; Tiwari, Prabhat

1995-01-01

A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

Spectroscopic study of the inhibition of calcium oxalate calculi by Larrea tridentata

NASA Astrophysics Data System (ADS)

Pinales, Luis Alonso

The causes of urolithiasis include such influences as diet, metabolic disorders, and genetic factors which have been documented as sources that aggravate urinary calculi depositions and aggregations, and, implicitly, as causes of urolithiasis. This study endeavors to detail the scientific mechanisms involved in calcium oxalate calculi formation, and, more importantly, their inhibition under growth conditions imposed by the traditional medicinal approach using the herbal extract, Larrea tridentata. The calculi were synthesized without and with Larrea tridentata infusion by employing the single diffusion gel technique. A visible decrease in calcium oxalate crystal growth with increasing amounts of Larrea tridentata herbal infusion was observed in photomicrographs, as well as a color change from white-transparent for pure crystals to light orange-brown for crystals with inhibitor. Analysis of the samples, which includes Raman, infrared absorption, scanning electron microscopy (SEM), and X-ray powder diffraction (XRD) techniques, demonstrate an overall transition in morphology of the crystals from monohydrate without herbal extract to dihydrate with inhibitor. Furthermore, the resulting data from Raman and infrared absorption support the possibilities of the influences, in this complex process, of NDGA and its derivative compounds from Larrea tridentata, and of the bonding of the magnesium of the inhibitor with the oxalate ion on the surface of the calculi crystals. This assumption corroborates well with the micrographs obtained under higher magnification, which show that the separated small crystallites consist of darker brownish cores, which we attribute to the dominance of growth inhibition by NDGA, surrounded by light transparent thin shells, which possibly correspond to passivation of the crystals by magnesium oxalate. The SEM results reveal the transformation from the dominant monoclinic structure of the calcium oxalate crystals grown alone to the tetragonal

Enzymatic mechanism of oxalate production in the TCA and glyoxylate pathways using various isolates of Antrodia radiculosa

Treesearch

K.M. Jenkins; S.V. Diehl; C.A. Clausen; F. Green

2011-01-01

Brown-rot fungi produce oxalate in large amounts; however, levels of accumulation and function vary by species. Copper-tolerant fungi, like Antrodia radiculosa, produce and accumulate high levels of oxalate in response to copper. Oxalate biosynthesis in copper-tolerant fungi has been linked to the glyoxylate and tricarboxylic acid (TCA) cycles. Within these two cycles...

Lattice vibrations and electronic transitions in the rare-earth metals: yttrium, gadolinium and lutetium.

PubMed

Olijnyk, Helmut

2005-01-12

Lattice vibrations in high-pressure phases of Y, Gd and Lu were studied by Raman spectroscopy. The observed phonon frequencies decrease towards the transitions to the dhcp and fcc phases. There is evidence that the entire structural sequence [Formula: see text] under pressure for the individual regular rare-earth metals and along the lanthanide series at ambient pressure involve softening of certain acoustic and optical phonon modes and of the elastic shear modulus C(44). Comparison is made to transitions between close-packed lattices in other metals, and possible correlations to s-d electron transfer are discussed.

The electrokinetic behavior of calcium oxalate monohydrate in macromolecular solutions

NASA Technical Reports Server (NTRS)

Curreri, P. A.; Onoda, G. Y., Jr.; Finlayson, B.

1988-01-01

Electrophoretic mobilities were measured for calcium oxalate monohydrate (COM) in solutions containing macromolecules. Two mucopolysaccharides (sodium heparin and chrondroitin sulfate) and two proteins (positively charged lysozyme and negatively charged bovine serum albumin) were studied as adsorbates. The effects of pH, calcium oxalate surface charge (varied by calcium or oxalate ion activity), and citrate concentration were investigated. All four macromolecules showed evidence for chemical adsorption. The macromolecule concentrations needed for reversing the surface charge indicated that the mucopopolysacchrides have greater affinity for the COM surface than the proteins. The amount of proteins that can chemically adsorb appears to be limited to approximately one monomolecular layer. When the surface charge is high, an insufficient number of proteins can chemically adsorb to neutralize or reverse the surface charge. The remaining surface charge is balanced by proteins held near the surface by longer range electrostatic forces only. Citrate ions at high concentrations appear to compete effectively with the negative protein for surface sites but show no evidence for competing with the positively charged protein.

Stability-indicating RP-HPLC method for the simultaneous determination of escitalopram oxalate and clonazepam.

PubMed

Kakde, Rajendra B; Satone, Dinesh D; Gadapayale, Kamalesh K; Kakde, Megha G

2013-07-01

The objective of the current study was to develop a validated, specific stability-indicating reversed-phase liquid chromatographic (LC) method for the quantitative determination of escitalopram oxalate and clonazepam and their related substances in bulk drugs and pharmaceutical dosage forms in the presence of degradation products. Forced degradation studies were performed on the pure drugs of escitalopram oxalate and clonazepam, as per the stress conditions prescribed by the International Conference on Harmonization (ICH) using acid, base, oxidation, thermal stress and photolytic degradation to show the stability-indicating power of the method. Significant degradation was observed during acid and alkaline hydrolysis and no degradation was observed in other stress conditions. The chromatographic method was optimized using the samples generated from forced degradation studies. Good resolution between the peaks corresponded to the active pharmaceutical ingredients, escitalopram oxalate and clonazepam, and degradation products from the analyte were achieved on an ODS Hypersil C18 column (250 × 4.6 mm) using a mobile phase consisting of a mixture of acetonitrile-50 mM phosphate buffer + 10 mM triethylamine (70:30, v/v). The detection was conducted at 268 nm. The limit of detection and the limit of quantitation for escitalopram oxalate and clonazepam were established. The stress test solutions were assayed against the qualified working standards of escitalopram oxalate and clonazepam, which indicated that the developed LC method was stability-indicating. Validation of the developed LC method was conducted as per ICH requirements. The developed LC method was found to be suitable to check the quality of bulk samples of escitalopram oxalate and clonazepam.

Evaluation of Oxalic Acid Treatments against the Mite Varroa destructor and Secondary Effects on Honey Bees Apis mellifera

PubMed Central

Adjlane, Noureddine; Tarek, El-Ounass; Haddad, Nizar

2016-01-01

Background: The Varroa destructor varroasis is a very serious parasite of honeybee Apis mellifera. The objective of this study was to evaluate the effectiveness of Varroa treatment using organic acid (oxalic acid) in Algeria identifying its side effects on bee colonies. Methods: Treatment was conducted in one apiary consisting 30 colonies kept in Langstroth hives kind. Oxalic acid dripped directly on bees 5ml of this solution of oxalic acid per lane occupied by a syringe. Three doses were tested: 4.2, 3.2 and 2.1% oxalic acid is 100, 75 and 50 g of oxalic acid dehydrate in one litter of sugar syrup (1water to1 surge) concentration. Results: The percentage of average efficiency obtained for the first dose was 81%, 72.19% for the second dose, and 65% for third one, while the dose of 100 g oxalic acid causes a weakening of honey bee colonies. Conclusion: The experiments revealed that clear variation in the treatment efficiency among colonies that this might be related to brood presence therefore in order to assure the treatment efficiency oxalic acid should be part of a bigger strategy of Varroa treatment. PMID:28032102

Oxalate-Metabolising Genes of the White-Rot Fungus Dichomitus squalens Are Differentially Induced on Wood and at High Proton Concentration

PubMed Central

de Vries, Ronald P.; Timonen, Sari; Hildén, Kristiina

2014-01-01

Oxalic acid is a prevalent fungal metabolite with versatile roles in growth and nutrition, including degradation of plant biomass. However, the toxicity of oxalic acid makes regulation of its intra- and extracellular concentration crucial. To increase the knowledge of fungal oxalate metabolism, a transcriptional level study on oxalate-catabolising genes was performed with an effective lignin-degrading white-rot fungus Dichomitus squalens, which has demonstrated particular abilities in production and degradation of oxalic acid. The expression of oxalic-acid decomposing oxalate decarboxylase (ODC) and formic-acid decomposing formate dehydrogenase (FDH) encoding genes was followed during the growth of D. squalens on its natural spruce wood substrate. The effect of high proton concentration on the regulation of the oxalate-catabolising genes was determined after addition of organic acid (oxalic acid) and inorganic acid (hydrochloric acid) to the liquid cultures of D. squalens. In order to evaluate the co-expression of oxalate-catabolising and manganese peroxidase (MnP) encoding genes, the expression of one MnP encoding gene, mnp1, of D. squalens was also surveyed in the solid state and liquid cultures. Sequential action of ODC and FDH encoding genes was detected in the studied cultivations. The odc1, fdh2 and fdh3 genes of D. squalens showed constitutive expression, whereas ODC2 and FHD1 most likely are the main responsible enzymes for detoxification of high concentrations of oxalic and formic acids. The results also confirmed the central role of ODC1 when D. squalens grows on coniferous wood. Phylogenetic analysis revealed that fungal ODCs have evolved from at least two gene copies whereas FDHs have a single ancestral gene. As a conclusion, the multiplicity of oxalate-catabolising genes and their differential regulation on wood and in acid-amended cultures of D. squalens point to divergent physiological roles for the corresponding enzymes. PMID:24505339

Dissolution kinetics and biodurability of tremolite particles in mimicked lung fluids: Effect of citrate and oxalate

NASA Astrophysics Data System (ADS)

Rozalen, Marisa; Ramos, M. Elena; Huertas, F. Javier; Fiore, Saverio; Gervilla, Fernando

2013-11-01

The effect of citrate and oxalate on tremolite dissolution rate was measured at 37 °C in non-stirred flow-through reactors, using modified Gamble's solutions at pH 4 (macrophages), 7.4 (interstitial fluids) and 5.5 (intermediate check point) containing 0, 0.15, 1.5 and 15 mmol L-1 of citrate or oxalate. The dissolution rates calculated from Si concentration in the output solutions without organic ligands depend on pH, decreasing when the pH increases from -13.00 (pH 4) to -13.35 (pH 7.4) mol g-1 s-1 and following a proton-promoted mechanism. The presence of both ligands enhances dissolution rates at every pH, increasing this effect when the ligand concentration increases. Citrate produces a stronger effect as a catalyst than oxalate, mainly at more acidic pHs and enhances dissolution rates until 20 times for solutions with 15 mmol L-1 citrate. However, at pH 7.4 the effect is lighter and oxalate solutions (15 mmol L-1) only enhances dissolution rates eight times respect to free organic ligand solutions. Dissolution is promoted by the attack to protons and organic ligands to the tremolite surface. Magnesium speciation in oxalate and citrate solutions shows that Mg citrate complexes are more effective than oxalate ones during the alteration of tremolite in magrophages, but this tendency is the opposite for interstitial fluids, being oxalate magnesium complexes stronger. The biodurability estimations show that the destruction of the fibers is faster in acidic conditions (macrophages) than in the neutral solutions (interstitial fluid). At pH 4, both ligands oxalate and citrate reduce the residence time of the fibers with respect to that calculated in absence of ligands. Nevertheless, at pH 7.4 the presence of ligands does not reduce significantly the lifetime of the fibers.

Mössbauer effect of 151Eu in europium oxalate and fluorides

NASA Astrophysics Data System (ADS)

Wynter, C. I.; Oliver, F. W.; Davis, Alfred; Spijkerman, J. J.; Stadelmaier, H.; Wolfe, E. A.

1993-04-01

In a short communication [C.I. Wynter et al., Radiochimica Acta 55 (1991) 111.] we reported "relative broadening factors" of europium fluoride (EuF 3), europium oxide (Eu 2O 3), europium oxalate decahydrate (Eu 2(C 2O 4) 3.10H 2O and europium benzoate tetrahydrate Eu(C 6H 5COO) 3.4H 2O. Indications of the "relative broadening factor" of the oxalate compared to the fluoride suggested that the oxalate may indeed be a better host for the 21.6-keV gamma ray transition than the fluoride. In a continuing search for a better host matrix for this Mössbauer transition, we have prepared additionally a systematic series of fluorides, namely. EuF 3, NaEuF 4, Na 3EuF 6, and K 3EuF 6 to measure the linewidths and compute the "true" broadening factor using the natural linewidth of 151Eu as 1.31 {mm}/{s}.

Determining the biochemical properties of the Oxalate Biosynthetic Component (Obc)1 from Burkholderia mallei

USDA-ARS?s Scientific Manuscript database

Oxalic acid is produced by a variety of organisms ranging from simple microbes to complex animals. This acid has been proposed to fulfill various physiological and pathological functions which vary between organisms. In bacteria from the Burkholderia genus, oxalate secretion has been shown to be quo...

Minerals with metal-organic framework structures

PubMed Central

Huskić, Igor; Pekov, Igor V.; Krivovichev, Sergey V.; Friščić, Tomislav

2016-01-01

Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals. PMID:27532051

Minerals with metal-organic framework structures.

PubMed

Huskić, Igor; Pekov, Igor V; Krivovichev, Sergey V; Friščić, Tomislav

2016-08-01

Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals.

Evaluation of soluble oxalates content in infusions of different kinds of tea and coffee available on the Polish market.

PubMed

Rusinek, Elzbieta

2012-01-01

Tea and coffee are the potentially rich source of oxalic acid, which can act as a antinutrient. The aim of this study was to determine and evaluate the content of soluble oxalates in teas and coffees available on the Polish market. The green, red and black teas, and black natural ground and instant coffees were used for preparing the infusions. The manganometric method was used for the determination of the oxalates in the infusions. The mean oxalates content in the infusions from 3 g of black teas was 115.68 mg/100 cm3 and was higher as compared to red teas (101.91 mg/100 cm3) and green teas (87.64 mg/100 cm3). Disregarding the variety of analyzed teas, the largest oxalates content was in infusions of pure one-component tea--"Sir Roger" (164.82-174.22 mg/100 cm3), while the lowest oxalates content was noted in the tea containing the components from other plants ("Bio-Active" with grapefruit juice--reaching as low level as 39.00 mg/100 cm3). Instant coffees contained larger amount of oxalates than natural ground coffees. Irrespective of the kind of the tested coffees, the lowest oxalates content was found in the infusions from the following coffees: Tchibo Exclusive--19.62 mg/100 cm3, Gala ulubiona--37.32 mg/100 cm3, and Maxwell House--38.40 mg/100 cm3, while the highest oxalates content in instant coffee--Nescafe Espiro 51.80 mg/100 cm3. The results revealed a significant relation between phytochemical composition of analyzed teas and coffees and the level of soluble oxalates in infusions prepared from the tested products.

Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

NASA Astrophysics Data System (ADS)

Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

2018-01-01

Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.