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Sample records for acids oxalic malonic

  1. Structural tuning of photoluminescence in nanoporous anodic alumina by hard anodization in oxalic and malonic acids

    NASA Astrophysics Data System (ADS)

    Santos, Abel; Alba, Maria; Rahman, Mahbubur M.; Formentín, Pilar; Ferré-Borrull, Josep; Pallarès, Josep; Marsal, Lluis F.

    2012-04-01

    We report on an exhaustive and systematic study about the photoluminescent properties of nanoporous anodic alumina membranes fabricated by the one-step anodization process under hard conditions in oxalic and malonic acids. This optical property is analysed as a function of several parameters (i.e. hard anodization voltage, pore diameter, membrane thickness, annealing temperature and acid electrolyte). This analysis makes it possible to tune the photoluminescent behaviour at will simply by modifying the structural characteristics of these membranes. This structural tuning ability is of special interest in such fields as optoelectronics, in which an accurate design of the basic nanostructures (e.g. microcavities, resonators, filters, supports, etc.) yields the control over their optical properties and, thus, upon the performance of the nanodevices derived from them (biosensors, interferometers, selective filters, etc.)

  2. Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

    NASA Astrophysics Data System (ADS)

    Medvedkov, Ya. A.; Serezhkina, L. B.; Grigor'ev, M. S.; Serezhkin, V. N.

    2016-05-01

    Two new malonate-containing uranyl complexes with carbamide of the formulas [UO2(C3H2O4)( Urea)2] ( I) and [UO2(C3H2O4)( Urea)3] ( II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO2(C2O4)( Urea)3] ( III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO2(C3H2O4)( Urea)2]∞ belonging to the crystal-chemical group AT 11 M 2 1 ( A = UO 2 2+ , T 11 = C3H2O 4 2- , M 1 = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO2( L)( Urea)3], where L = C3H2O 4 2- or C2O 4 2- , belonging to the crystal-chemical group AB 01 M 3 1 ( A = UO 2 2+ , B 01 = C3H2O 4 2- or C2O 4 2- , M 1 = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi-Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.

  3. Mechanistic studies of malonic acid-mediated in situ acylation.

    PubMed

    Chandra, Koushik; Naoum, Johnny N; Roy, Tapta Kanchan; Gilon, Chaim; Gerber, R Benny; Friedler, Assaf

    2015-09-01

    We have previously introduced an easy to perform, cost-effective and highly efficient acetylation technique for solid phase synthesis (SPPS). Malonic acid is used as a precursor and the reaction proceeds via a reactive ketene that acetylates the target amine. Here we present a detailed mechanistic study of the malonic acid-mediated acylation. The influence of reaction conditions, peptide sequence and reagents was systematically studied. Our results show that the methodology can be successfully applied to different types of peptides and nonpeptidic molecules irrespective of their structure, sequence, or conformation. Using alkyl, phenyl, and benzyl malonic acid, we synthesized various acyl peptides with almost quantitative yields. The ketenes obtained from the different malonic acid derived precursors were characterized by in situ (1) H-NMR. The reaction proceeded in short reaction times and resulted in excellent yields when using uronium-based coupling agents, DIPEA as a base, DMF/DMSO/NMP as solvents, Rink amide/Wang/Merrifield resins, temperature of 20°C, pH 8-12 and 5 min preactivation at inert atmosphere. The reaction was unaffected by Lewis acids, transition metal ions, surfactants, or salt. DFT studies support the kinetically favorable concerted mechanism for CO2 and ketene formation that leads to the thermodynamically stable acylated products. We conclude that the malonic acid-mediated acylation is a general method applicable to various target molecules. PMID:25846609

  4. Direct Catalytic Asymmetric Synthesis of β-Hydroxy Acids from Malonic Acid.

    PubMed

    Gao, Hang; Luo, Zhenli; Ge, Pingjin; He, Junqian; Zhou, Feng; Zheng, Peipei; Jiang, Jun

    2015-12-18

    A nickel(II) catalyzed asymmetric synthesis of β-hydroxy acids from malonic acid and ketones was developed, revealing for the first time the synthetic utility of malonic acid in the construction of chiral carboxyl acids; importantly, the synthetic potential of this strategy was further demonstrated by the rapid construction of cephalanthrin A, phaitanthrin B, cruciferane, and rice metabolites.

  5. Quantum studies of deprotonated forms of malonic acid

    NASA Astrophysics Data System (ADS)

    Asciutto, Eliana; Lee, Jung Goo; Pedersen, Lee G.; Sagui, Celeste

    2004-03-01

    There have been numerous computational studies on carboxylic acids, specially in the simplest ones (formic and acetic acids). A considerable amount of these computations has been dedicated towards developing an understanding of proton transfer. In this work we study malonate as a model for γ-carboxyglutamic acid (Gla). Gla is a metal-binding amino acid whose synthesis is dependent upon vitamin K. Of the classes of proteins that contain Gla, the vitamin K-dependent blood coagulation and regulatory proteins have have been most thoroughly studied. The Gla domain in these proteins (generally consisting of 10-12 Gla residues) induces an structure that facilitates calcium-mediated interactions of the protein with membrane surfaces. In order to get a better understanding of this fundamental role of Gla at a quantum level, we study the role of intramolecular proton transfer in malonate in its divalent anionic form. The di-anion is particularly challenging. A correct description of the potential energy hypersurface is obtained only by application of large basis sets in conjunction with methods including high-level treatment of electron correlation effects.

  6. Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

    USGS Publications Warehouse

    Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

    2001-01-01

    Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

  7. Surface behavior of malonic acid adsorption at the air/water interface.

    PubMed

    Blower, Patrick G; Shamay, Eric; Kringle, Loni; Ota, Stephanie T; Richmond, Geraldine L

    2013-03-28

    The presence of organic materials adsorbed to the surfaces of aerosol particles has been demonstrated to be a determining factor in relevant atmospheric processes. Malonic acid is a small, water-soluble organic acid that is common in aerosols and is surface-active. A comprehensive investigation of the adsorption of malonic acid to the air/water interface was accomplished using vibrational sum frequency spectroscopy (VSFS) and surface tension measurements as functions of concentration and pH. Malonic acid was found to be weakly solvated at the air/water interface, and its orientation as a function of concentration was explored through different VSFS polarization schemes. pH-dependent experiments revealed that the surface-active species is the fully protonated species. Computational analyses were used to obtain depth-specific geometries of malonic acid at the air/water interface that confirm and enrich the experimental results. PMID:23384061

  8. Malonic acid suppresses mucin-type O-glycan degradation during hydrazine treatment of glycoproteins.

    PubMed

    Goso, Yukinobu

    2016-03-01

    Hydrazine treatment is frequently used for releasing mucin-type O-glycans (O-glycans) from glycoproteins because the method provides O-glycans that retain a reducible GalNAc at their reducing end, which is available for fluorescent labeling. However, many O-glycans are degraded by "peeling" during this treatment. In the current study, it was found that malonic acid suppressed O-glycan degradation during hydrazine treatment of bovine fetuin or porcine gastric mucin in both the gas and liquid phases. This is paradoxical because the release of O-glycans from glycoproteins occurs under alkaline conditions. However, malonic acid seems to prevent the degradation through its acidic property given that other weak acids also prevented the degradation. Accordingly, disodium malonate did not suppress O-glycan degradation. Application of this method to rat gastric mucin demonstrated that the majority of the major O-glycans obtained in the presence of malonic acid were intact, whereas those obtained in the absence of malonic acid were degraded. These results suggest that hydrazine treatment in the presence of malonic acid would allow glycomic analysis of native mucin glycoproteins.

  9. Observations of sharp oxalate reductions in stratocumulus clouds at variable altitudes: organic acid and metal measurements during the 2011 E-PEACE campaign.

    PubMed

    Sorooshian, Armin; Wang, Zhen; Coggon, Matthew M; Jonsson, Haflidi H; Ervens, Barbara

    2013-07-16

    This work examines organic acid and metal concentrations in northeastern Pacific Ocean stratocumulus cloudwater samples collected by the CIRPAS Twin Otter between July and August 2011. Correlations between a suite of various monocarboxylic and dicarboxylic acid concentrations are consistent with documented aqueous-phase mechanistic relationships leading up to oxalate production. Monocarboxylic and dicarboxylic acids exhibited contrasting spatial profiles reflecting their different sources; the former were higher in concentration near the continent due to fresh organic emissions. Concentrations of sea salt crustal tracer species, oxalate, and malonate were positively correlated with low-level wind speed suggesting that an important route for oxalate and malonate entry in cloudwater is via some combination of association with coarse particles and gaseous precursors emitted from the ocean surface. Three case flights show that oxalate (and no other organic acid) concentrations drop by nearly an order of magnitude relative to samples in the same vicinity. A consistent feature in these cases was an inverse relationship between oxalate and several metals (Fe, Mn, K, Na, Mg, Ca), especially Fe. By means of box model studies we show that the loss of oxalate due to the photolysis of iron oxalato complexes is likely a significant oxalate sink in the study region due to the ubiquity of oxalate precursors, clouds, and metal emissions from ships, the ocean, and continental sources.

  10. Ultrasonic degradation of oxalic acid in aqueous solutions.

    PubMed

    Dükkanci, M; Gündüz, G

    2006-09-01

    This paper describes the ultrasonic degradation of oxalic acid. The effects of ultrasonic power, H(2)O(2), NaCl, external gases on the degradation of oxalic acid were investigated. Reactor flask containing oxalic acid was immersed in the ultrasonic bath with water as the coupling fluid. Representative samples withdrawn were analysed by volumetric titration. Degradation degree of oxalic acid increased with increasing ultrasonic power. It was observed that H(2)O(2) has negative contribution on the degradation of oxalic acid and there was an optimum concentration of NaCl for enhancing the degradation degree of oxalic acid. Although bubbling nitrogen gave higher degradation than that for bubbling air, both gases (for 20 min before sonication and during sonication together) could not help to enhance the degradation of oxalic acid when compared with the degradation without gas passage. PMID:16352455

  11. Red facts: Oxalic acid. Fact sheet

    SciTech Connect

    Not Available

    1992-12-01

    All pesticides sold or used in the United States must be registered by EPA, based on scientific studies showing that they can be used without posing unreasonable risks to people or the environment. Because of advances in scientific knowledge, the law requires that pesticides which were first registered years ago be reregistered to ensure that they meet today's more stringent standards. Oxalic acid is registered for use as a disinfectant to control bacteria and germs, and as a sanitizer, in toilet bowls, urinals and bathroom premises. Oxalic acid also has many diverse, non-pesticidal, manufacturing and industrial uses including use in fabric printing and dyeing; bleaching straw hats; removing paint, varnish, rust or ink stains; and cleaning wood.

  12. The oxalic acid: 2-chloroacetamide crystallization: A new revelation

    NASA Astrophysics Data System (ADS)

    Chitra, R.; Choudhury, R. R.; Capet, Frederic; Roussel, Pascal

    2013-02-01

    The OH of COOH can acts as both donor and acceptor of hydrogen bond. OH of COOH as an acceptor was primarily observed in Oxalic acid Amide complexes. In order to further understand the packing in these complexes, oxalic acid was complexed with 2-tricholoroacetamide. This crystallization resulted in the formation of ammonium tetraoxalate dehydrate. A result similar to what was observed in complexation of oxalic acid with amide containing amino acids (asparagine and glutamine). Interestingly in all these cases, the amide bond is broken, to form the ammonium ion when trying to complex with oxalic acid.

  13. Kinetic study of oxalic acid inhibition on enzymatic browning.

    PubMed

    Son, S M; Moon, K D; Lee, C Y

    2000-06-01

    Oxalic acid has a strong antibrowning activity. The inhibitory pattern on catechol-PPO model system appeared to be competitive, with a K(i) value of 2.0 mM. When the PPO was incubated with oxalic acid, the activity was not recovered via dialysis, but the inactivated enzyme partially recovered its activity when cupric ion was added. Comparing the relative antibrowning effectiveness of oxalic acid with other common antibrowning agents, oxalic acid with I(50) value of 1.1 mM is as effective as kojic acid and more potent than cysteine and glutathione.

  14. 1,3-Propanediol Made From Fermentation-Derived Malonic Acid: Office of Industrial Technologies (OIT) Agriculture Project Fact Sheet

    SciTech Connect

    Carde, T.

    2001-09-12

    1,3-Propanediol is one of two ingredients used in producing polytrimethylene terephthalate (PTT), a polymer which can be used in polyester and nylon applications. Researchers are developing a process to ferment biomass feedstock to malonic acid using filamentous fungi and then catalytically convert malonic acid to 1,3-propanediol.

  15. Reregistration eligibility document (RED): Oxalic acid

    SciTech Connect

    Not Available

    1992-12-01

    EPA is directed by the Federal Insecticide, Fungicide, and Rodenticide Act as amended in 1988 (FIFRA '88) to review all pesticide products containing active ingredients initially registered before November 1, 1984, and to reregister those products that have a substantially complete data base and do not pose unreasonable adverse effects to people or the environment. This pesticide reregistration program is to be completed by the late 1990's. The Reregistration Eligibility Document (or RED) for oxalic acid discusses the scientific data and other information supporting EPA's regulatory conclusion that products containing a pesticide do not pose unreasonable risks when used as directed by Agency-approved labeling, and are eligible for reregistration.

  16. 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.

  17. Oxalic acid degradation by a novel fungal oxalate oxidase from Abortiporus biennis.

    PubMed

    Grąz, Marcin; Rachwał, Kamila; Zan, Radosław; Jarosz-Wilkołazka, Anna

    2016-01-01

    Oxalate oxidase was identified in mycelial extracts of a basidiomycete Abortiporus biennis strain. Intracellular enzyme activity was detected only after prior lowering of the pH value of the fungal cultures by using oxalic or hydrochloric acids. This enzyme was purified using size exclusion chromatography (Sephadex G-25) and ion-exchange chromatography (DEAE-Sepharose). This enzyme exhibited optimum activity at pH 2 when incubated at 40°C, and the optimum temperature was established at 60°C. Among the tested organic acids, this enzyme exhibited specificity only towards oxalic acid. Molecular mass was calculated as 58 kDa. The values of Km for oxalate and Vmax for the enzyme reaction were 0.015 M and 30 mmol min(-1), respectively. PMID:27337220

  18. Oxalic acid decreases calcium absorption in rats

    SciTech Connect

    Weaver, C.M.; Martin, B.R.; Ebner, J.S.; Krueger, C.A.

    1987-11-01

    Calcium absorption from salts and foods intrinsically labeled with /sup 45/Ca was determined in the rat model. Calcium bioavailability was nearly 10 times greater for low oxalate kale, CaCO/sub 3/ and CaCl/sub 2/ than from CaC/sub 2/O/sub 4/ (calcium oxalate) and spinach (high in oxalates). Extrinsic and intrinsic labeling techniques gave a similar assessment of calcium bioavailability from kale but not from spinach.

  19. Spectroscopic Evidence of Keto-enol Tautomerism in Deliquesced Malonic Acid Particles

    SciTech Connect

    Ghorai, Suman; Laskin, Alexander; Tivanski, Alexei V.

    2011-04-11

    Scanning Transmission X-ray Microscopy combined with Near Edge X-ray Absorption Fine Structure Spectroscopy (STXM/NEXAFS), and optical microscopy coupled with Fourier Transform Infrared Spectroscopy (micro-FTIR) have been applied to observe hygroscopic growth and chemical changes in malonic acid particles deposited on substrates. Extent of the hygroscopic growth of particles has been quantified in terms of the corresponding water-to-solute ratios (WSR) based on STXM/NEXAFS and micro-FTIR data sets. WSR values derived separately from two applied methods displayed a remarkable agreement with previous data reported in the literature. Comparison of NEXAFS and FTIR spectra acquired at different relative humidity (RH) shows efficient keto-enol tautomerization of malonic acid, with the enol form dominated at higher RH. The keto-enol equilibrium constants were calculated using relevant peak intensities in the carbon and oxygen K-edge NEXAFS spectra as a function of RH.

  20. Production of oxalic acid by some fungi infected tubers.

    PubMed

    Faboya, O; Ikotun, T; Fatoki, O S

    1983-01-01

    Oxalic acid (as oxalate) was detected in four tubers commonly used for food in Nigeria-Dioscorea rotundata (White yam), Solanum tuberosum (Irish potato), Ipomoea batatas (Sweet potato), and Manihot esculenta (cassava). Whereas healthy I. batata had the highest oxalic acid content, healthy M. esculenta contained the lowest. When all tubers were artifically inoculated with four fungi-Penicillium oxalicum CURIE and THOM, Aspergillus niger VAN TIEGH, A. flavus and A. tamarii KITA, there was an increase in oxalate content/g of tuber tissue. The greatest amount of oxalate was produced by P. oxalicum in D. rotundata tuber. Consistently higher amounts of oxalate were produced by the four fungi in infected sweet potato tuber than in any other tuber and consistently lower amounts of oxalate were produced by the four fungi in Irish potato tuber. Differences in the carbohydrate type present in the tubers and in the biosynthesis pathway are thought to be responsible for variation in the production of oxalate in the different tubers by the four fungi used.

  1. Production and degradation of oxalic acid by brown rot fungi

    SciTech Connect

    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. 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.

  2. Production and Degradation of Oxalic Acid by Brown Rot Fungi

    PubMed Central

    Espejo, Eduardo; Agosin, Eduardo

    1991-01-01

    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 14C-labeled oxalic acid to CO2 during cellulose depolymerization. The other brown rot fungi also oxidized 14C-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. 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 14C-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. PMID:16348522

  3. Oxalic acid, epsom salt and the poison bottle.

    PubMed

    Campbell, W A

    1982-03-01

    1 During the 19th century inadequate control of the sale of poisons, widespread illiteracy, and the English addiction to self-medication contributed to the high incidence of accidental poisoning by oxalic acid mistaken for Epsom salt. 2 Chemical methods for identifying oxalic acid failed when the product was adulterated. 3 Many mechanical devices were proposed to prevent careless dispensing; designs for poison bottles of distinctive shape, colour and texture appeared regularly for 40 years. PMID:6757103

  4. Modeling of Turing Structures in the Chlorite-Iodide-Malonic Acid-Starch Reaction System

    NASA Astrophysics Data System (ADS)

    Lengyel, Istivan; Epstein, Irving R.

    1991-02-01

    Recent experiments on the chlorite-iodide-malonic acid-starch reaction in a gel reactor give the first evidence of the existence of the symmetry breaking, reaction-diffusion structures predicted by Turing in 1952. A five-variable model that describes the temporal behavior of the system is reduced to a two-variable model, and its spatial behavior is analyzed. Structures have been found with wavelengths that are in good agreement with those observed experimentally. The gel plays a key role by binding key iodine species, thereby creating the necessary difference in the effective diffusion coefficients of the activator and inhibitor species, iodide and chlorite ions, respectively.

  5. Means for reducing oxalic acid to a product

    SciTech Connect

    Morduchowitz, A.; Sammells, A.F.

    1988-12-06

    This patent describes an apparatus for reducing oxalic acid to a product comprising: a cell including a separator for separating the cell into two chambers, a catholyte chamber and an anolyte chamber, each chamber having an inlet and an outlet; a porous anode arranged within the anolyte section in a manner so that an electrolyte entering through the inlet of the anolyte section will pass through the anode and exit through the outlet of the anolyte section; means for providing an electrolyte to the inlet of the anolyte chamber in a manner so that it will exit through the outlet of the anolyte chamber; means for providing a mixture of oxalic acid and an electrolyte to the inlet of the catholyte chamber; porous cathode means located in the catholyte chamber for reducing the oxalic acid in the oxalic acid-electrolyte mixture to the product within the cathode means when a d.c. voltage provided across the anode and the cathode means, the product exiting the cell by way of the catholyte chamber's outlet; and means for providing a d.c. voltage across the cathode means and the anode so as to cooperate in the reduction of the oxalic acid; and in which the cathode means includes a porous cathode having discrete sites of platinum and mercury as catalysts and the product is ethylene glycol.

  6. Oxalic acid adsorption states on the clean Cu(110) surface

    NASA Astrophysics Data System (ADS)

    Fortuna, Sara

    2016-11-01

    Carboxylic acids are known to assume a variety of configurations on metallic surfaces. In particular oxalic acid on the Cu(110) surface has been proposed to assume a number of upright configurations. Here we explore with DFT calculations the possible structures that oxalic acid can form on copper 110 at different protonation states, with particular attention at the possibility of forming structures composed of vertically standing molecules. In its fully protonated form it is capable of anchoring itself on the surface thanks to one of its hydrogen-free oxygens. We show the monodeprotonated upright molecule with two oxygens anchoring it on the surface to be the lowest energy conformation of a single oxalic molecules on the Cu(110) surface. We further show that it is possible for this configuration to form dense hexagonally arranged patterns in the unlikely scenario in which adatoms are not involved.

  7. 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

  8. Radioiodinated Phenylalkyl Malonic Acid Derivatives as pH-Sensitive SPECT Tracers

    PubMed Central

    Bauwens, Matthias; De Saint-Hubert, Marijke; Cleynhens, Jan; Brams, Laura; Devos, Ellen; Mottaghy, Felix M.; Verbruggen, Alfons

    2012-01-01

    Introduction In vivo pH imaging has been a field of interest for molecular imaging for many years. This is especially important for determining tumor acidity, an important driving force of tumor invasion and metastasis formation, but also in the process of apoptosis. Methods 2-(4-[123I]iodophenethyl)-2-methylmalonic acid (IPMM), 2-(4-[123I]iodophenethyl)-malonic acid (IPM), 2-(4-[123I]iodobenzyl)-malonic acid (IBMM) and 4-[123I]iodophthalic acid (IP) were radiolabeled via the Cu+ isotopic nucleophilic exchange method. All tracers were tested in vitro in buffer systems to assess pH driven cell uptake. In vivo biodistribution of [123I]IPMM and [123I]IPM was determined in healthy mice and the pH targeting efficacy in vivo of [123I]IPM was evaluated in an anti-Fas monoclonal antibody (mAb) apoptosis model. In addition a mouse RIF-1 tumor model was explored in which tumor pH was decreased from 7.0 to 6.5 by means of induction of hyperglycemia in combination with administration of meta-iodobenzylguanidine. Results Radiosynthesis resulted in 15–20% for iodo-bromo exchange and 50–60% yield for iodo-iodo exchange while in vitro experiments showed a pH-sensitive uptake for all tracers. Shelf-life stability and in vivo stability was excellent for all tracers. [123I]IPMM and [123I]IPM showed a moderately fast predominantly biliary clearance while a high retention was observed in blood. The biodistribution profile of [123I]IPM was found to be most favorable in view of pH-specific imaging. [123I]IPM showed a clear pH-related uptake pattern in the RIF-1 tumor model. Conclusion Iodine-123 labeled malonic acid derivates such as [123I]IPM show a clearly pH dependent uptake in tumor cells both in vitro and in vivo which allows to visualize regional acidosis. However, these compounds are not suitable for detection of apoptosis due to a poor acidosis effect. PMID:22719886

  9. Solubility of the Sodium and Ammonium Salts of Oxalic Acid in Water with Ammonium Sulfate.

    PubMed

    Buttke, Lukas G; Schueller, Justin R; Pearson, Christian S; Beyer, Keith D

    2016-08-18

    The solubility of the sodium and ammonium salts of oxalic acid in water with ammonium sulfate present has been studied using differential scanning calorimetry, X-ray crystallography, and infrared spectroscopy. The crystals that form from aqueous mixtures of ammonium sulfate/sodium hydrogen oxalate were determined to be sodium hydrogen oxalate monohydrate under low ammonium sulfate conditions and ammonium hydrogen oxalate hemihydrate under high ammonium sulfate conditions. Crystals from aqueous mixtures of ammonium sulfate/sodium oxalate were determined to be ammonium oxalate monohydrate under moderate to high ammonium sulfate concentrations and sodium oxalate under low ammonium sulfate concentrations. It was also found that ammonium sulfate enhances the solubility of the sodium oxalate salts (salting in effect) and decreases the solubility of the ammonium oxalate salts (salting out effect). In addition, a partial phase diagram for the ammonium hydrogen oxalate/water system was determined.

  10. Solubility of the Sodium and Ammonium Salts of Oxalic Acid in Water with Ammonium Sulfate.

    PubMed

    Buttke, Lukas G; Schueller, Justin R; Pearson, Christian S; Beyer, Keith D

    2016-08-18

    The solubility of the sodium and ammonium salts of oxalic acid in water with ammonium sulfate present has been studied using differential scanning calorimetry, X-ray crystallography, and infrared spectroscopy. The crystals that form from aqueous mixtures of ammonium sulfate/sodium hydrogen oxalate were determined to be sodium hydrogen oxalate monohydrate under low ammonium sulfate conditions and ammonium hydrogen oxalate hemihydrate under high ammonium sulfate conditions. Crystals from aqueous mixtures of ammonium sulfate/sodium oxalate were determined to be ammonium oxalate monohydrate under moderate to high ammonium sulfate concentrations and sodium oxalate under low ammonium sulfate concentrations. It was also found that ammonium sulfate enhances the solubility of the sodium oxalate salts (salting in effect) and decreases the solubility of the ammonium oxalate salts (salting out effect). In addition, a partial phase diagram for the ammonium hydrogen oxalate/water system was determined. PMID:27482644

  11. Atmospheric oxalic acid and related secondary organic aerosols in Qinghai Lake, a continental background site in Tibet Plateau

    NASA Astrophysics Data System (ADS)

    Meng, Jingjing; Wang, Gehui; Li, Jianjun; Cheng, Chunlei; Cao, Junji

    2013-11-01

    Summertime PM2.5 aerosols collected from Qinghai Lake (3200 m a.s.l.), a remote continental site in the northeastern part of Tibetan Plateau, were analyzed for dicarboxylic acids (C2-C11), ketocarboxylic acids and α-dicarbonyals. Oxalic acid (C2) is the dominant dicarboxylic acid in the samples, followed by malonic, succinic and azelaic acids. Total dicarboxylic acids (231 ± 119 ng m-3), ketocarboxylic acids (8.4 ± 4.3 ng m-3), and α-dicarbonyls (2.7 ± 2.1 ng m-3) at the Tibetan background site are 2-5 times less than those detected in lowland areas such as 14 Chinese megacities. Compared to those in other urban and marine areas enhancements in relative abundances of C2/total diacids and diacids-C/WSOC of the PM2.5 samples suggest that organic aerosols in the region are more oxidized due to strong solar radiation. Molecular compositions and air mass trajectories demonstrate that the above secondary organic aerosols in the Qinghai Lake atmosphere are largely derived from long-range transport. Ratios of oxalic acid, glyoxal and methylglyoxal to levoglucosan in PM2.5 aerosols emitted from household burning of yak dung, a major energy source for Tibetan in the region, are 30-400 times lower than those in the ambient air, which further indicates that primary emission from biomass burning is a negligible source of atmospheric oxalic acid and α-dicarbonyls at this background site.

  12. GADOLINIUM OXALATE SOLUBILITY MEASUREMENTS IN NITRIC ACID SOLUTIONS

    SciTech Connect

    Pierce, R.

    2012-02-22

    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 the 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}. For 6 M HNO{sub 3}, 10.5 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 g/L and 0.25 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}.

  13. Oxalic acid production by citric acid-producing Aspergillus niger overexpressing the oxaloacetate hydrolase gene oahA.

    PubMed

    Kobayashi, Keiichi; Hattori, Takasumi; Honda, Yuki; Kirimura, Kohtaro

    2014-05-01

    The filamentous fungus Aspergillus niger is used worldwide in the industrial production of citric acid. However, under specific cultivation conditions, citric acid-producing strains of A. niger accumulate oxalic acid as a by-product. Oxalic acid is used as a chelator, detergent, or tanning agent. Here, we sought to develop oxalic acid hyperproducers using A. niger as a host. To generate oxalic acid hyperproducers by metabolic engineering, transformants overexpressing the oahA gene, encoding oxaloacetate hydrolase (OAH; EC 3.7.1.1), were constructed in citric acid-producing A. niger WU-2223L as a host. The oxalic acid production capacity of this strain was examined by cultivation of EOAH-1 under conditions appropriate for oxalic acid production with 30 g/l glucose as a carbon source. Under all the cultivation conditions tested, the amount of oxalic acid produced by EOAH-1, a representative oahA-overexpressing transformant, exceeded that produced by A. niger WU-2223L. A. niger WU-2223L and EOAH-1 produced 15.6 and 28.9 g/l oxalic acid, respectively, during the 12-day cultivation period. The yield of oxalic acid for EOAH-1 was 64.2 % of the maximum theoretical yield. Our method for oxalic acid production gave the highest yield of any study reported to date. Therefore, we succeeded in generating oxalic acid hyperproducers by overexpressing a single gene, i.e., oahA, in citric acid-producing A. niger as a host.

  14. GADOLINIUM OXALATE SOLUBILITY MEASUREMENTS IN NITRIC ACID SOLUTIONS

    SciTech Connect

    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 the 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 Gd at 10

  15. Surface modification of polyvinyl alcohol/malonic acid nanofibers by gaseous dielectric barrier discharge plasma for glucose oxidase immobilization

    NASA Astrophysics Data System (ADS)

    Afshari, Esmail; Mazinani, Saeedeh; Ranaei-Siadat, Seyed-Omid; Ghomi, Hamid

    2016-11-01

    Polymeric nanofiber prepares a suitable situation for enzyme immobilization for variety of applications. In this research, we have fabricated polyvinyl alcohol (PVA)/malonic acid nanofibers using electrospinning. After fabrication of nanofibers, the effect of air, nitrogen, CO2, and argon DBD (dielectric barrier discharge) plasmas on PVA/malonic acid nanofibers were analysed. Among them, air plasma had the most significant effect on glucose oxidase (GOx) immobilization. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrum analysis and X-ray photoelectron spectroscopy (XPS) results revealed that in case of air plasma modified nanofibers, the carboxyl groups on the surface are increased. The scanning electron microscopy (SEM) images showed that, after GOx immobilization, the modified nanofibers with plasma has retained its nanofiber structure. Finally, we analysed reusability and storage stability of GOx immobilized on plasma modified and unmodified nanofibers. The results were more satisfactory for modified nanofibers with respect to unmodified ones.

  16. Crystal structure of di­methyl­ammonium hydrogen oxalate hemi(oxalic acid)

    PubMed Central

    Diallo, Waly; Gueye, Ndongo; Crochet, Aurélien; Plasseraud, Laurent; Cattey, Hélène

    2015-01-01

    Single crystals of the title salt, Me2NH2 +·HC2O4 −·0.5H2C2O4, were isolated as a side product from the reaction involving Me2NH, H2C2O4 and Sn(n-Bu)3Cl in a 1:2 ratio in methanol or by the reaction of the (Me2NH2)2C2O4 salt and Sn(CH3)3Cl in a 2:1 ratio in ethanol. The asymmetric unit comprises a di­methyl­ammonium cation (Me2NH2 +), an hydrogenoxalate anion (HC2O4 −), and half a mol­ecule of oxalic acid (H2C2O4) situated about an inversion center. From a supra­molecular point of view, the three components inter­act together via hydrogen bonding. The Me2NH2 + cations and the HC2O4 − anions are in close proximity through bifurcated N—H⋯(O,O) hydrogen bonds, while the HC2O4 − anions are organized into infinite chains via O—H⋯O hydrogen bonds, propagating along the a-axis direction. In addition, the oxalic acid (H2C2O4) mol­ecules play the role of connectors between these chains. Both the carbonyl and hydroxyl groups of each diacid are involved in four inter­molecular inter­actions with two Me2NH2 + and two HC2O4 − ions of four distinct polymeric chains, via two N—H⋯O and two O—H⋯O hydrogen bonds, respectively. The resulting mol­ecular assembly can be viewed as a two-dimensional bilayer-like arrangement lying parallel to (010), and reinforced by a C—H⋯O hydrogen bond. PMID:25995858

  17. Crystal structure of di-methyl-ammonium hydrogen oxalate hemi(oxalic acid).

    PubMed

    Diallo, Waly; Gueye, Ndongo; Crochet, Aurélien; Plasseraud, Laurent; Cattey, Hélène

    2015-05-01

    Single crystals of the title salt, Me2NH2 (+)·HC2O4 (-)·0.5H2C2O4, were isolated as a side product from the reaction involving Me2NH, H2C2O4 and Sn(n-Bu)3Cl in a 1:2 ratio in methanol or by the reaction of the (Me2NH2)2C2O4 salt and Sn(CH3)3Cl in a 2:1 ratio in ethanol. The asymmetric unit comprises a di-methyl-ammonium cation (Me2NH2 (+)), an hydrogenoxalate anion (HC2O4 (-)), and half a mol-ecule of oxalic acid (H2C2O4) situated about an inversion center. From a supra-molecular point of view, the three components inter-act together via hydrogen bonding. The Me2NH2 (+) cations and the HC2O4 (-) anions are in close proximity through bifurcated N-H⋯(O,O) hydrogen bonds, while the HC2O4 (-) anions are organized into infinite chains via O-H⋯O hydrogen bonds, propagating along the a-axis direction. In addition, the oxalic acid (H2C2O4) mol-ecules play the role of connectors between these chains. Both the carbonyl and hydroxyl groups of each diacid are involved in four inter-molecular inter-actions with two Me2NH2 (+) and two HC2O4 (-) ions of four distinct polymeric chains, via two N-H⋯O and two O-H⋯O hydrogen bonds, respectively. The resulting mol-ecular assembly can be viewed as a two-dimensional bilayer-like arrangement lying parallel to (010), and reinforced by a C-H⋯O hydrogen bond.

  18. Nanomolar CFTR inhibition by pore-occluding divalent polyethylene glycol-malonic acid hydrazides.

    PubMed

    Sonawane, N D; Zhao, Dan; Zegarra-Moran, Olga; Galietta, Luis J V; Verkman, A S

    2008-07-21

    Inhibitors of the cystic fibrosis transmembrane conductance regulator (CFTR) chloride channel have potential application as antisecretory therapy in cholera. We synthesized mono- and divalent CFTR inhibitors consisting of a malonic acid hydrazide (MalH) coupled via a disulfonic stilbene linker to polyethylene glycols (PEGs; 0.2-100 kDa). IC50 values for CFTR inhibition were 10-15 microM for the monovalent MalH-PEGs, but substantially lower for divalent MalH-PEG-MalH compounds, decreasing from 1.5 to 0.3 microM with increasing PEG size and showing positive cooperativity. Whole-cell patch-clamp showed voltage-dependent CFTR block with inward rectification. Outside-out patch-clamp showed shortened single-channel openings, indicating CFTR pore block from the extracellular side. Luminally added MalH-PEG-MalH blocked by >90% cholera toxin-induced fluid secretion in mouse intestinal loops (IC50 approximately 10 pmol/loop), and greatly reduced mortality in a suckling mouse cholera model. These conjugates may provide safe, inexpensive antisecretory therapy. PMID:18635008

  19. Oxalic acid-mediated stress responses in Brassica napus L.

    PubMed

    Liang, Yue; Strelkov, Stephen E; Kav, Nat N V

    2009-06-01

    Oxalic acid (OA) occurs extensively in nature and plays diverse roles, especially in pathogenic processes involving various plant pathogens. However, proteome changes and modifications of signaling and oxidative network of plants in response to OA are not well understood. In order to investigate the responses of Brassica napus toward OA, a proteome analysis was conducted employing 2-DE with MS/MS. A total of 37 proteins were identified as responding to OA stress, of which 13 were up-regulated and 24 were down-regulated. These proteins were categorized into several functional groups including protein processing, RNA processing, photosynthesis, signal transduction, stress response, and redox homeostasis. Investigation of the effect of OA on phytohormone signaling and oxidative responses revealed that jasmonic acid-, ethylene-, and abscisic acid-mediated signaling pathways appear to increase at later time points, whereas those pathways mediated by salicylic acid appear to be suppressed. Moreover, the activities of the antioxidant enzymes catalase, peroxidase, superoxide dismutase and oxalic acid oxidase, but not NADPH oxidase, were suppressed by OA stress. Our findings are discussed within the context of the proposed role(s) of OA during infection by Sclerotinia sclerotiorum and subsequent disease progression. PMID:19526549

  20. Oxalic Acid Has an Additional, Detoxifying Function in Sclerotinia sclerotiorum Pathogenesis

    PubMed Central

    Heller, Annerose; Witt-Geiges, Tanja

    2013-01-01

    The mechanism of the diseases caused by the necrotroph plant pathogen Sclerotinia sclerotiorum is not well understood. To investigate the role of oxalic acid during infection high resolution, light-, scanning-, transmission electron microscopy and various histochemical staining methods were used. Our inoculation method allowed us to follow degradation of host plant tissue around single hyphae and to observe the reaction of host cells in direct contact with single invading hyphae. After penetration the outer epidermal cell wall matrix appeared degraded around subcuticular hyphae (12-24 hpi). Calcium oxalate crystals were detected in advanced (36-48 hpi) and late (72 hpi) infection stages, but not in early stages. In early infection stages, surprisingly, no toxic effect of oxalic acid eventually secreted by S. sclerotiorum was observed. As oxalic acid is a common metabolite in plants, we propose that attacked host cells are able to metabolize oxalic acid in the early infection stage and translocate it to their vacuoles where it is stored as calcium oxalate. The effects, observed on healthy tissue upon external application of oxalic acid to non-infected, living tissue and cell wall degradation of dead host cells starting at the inner side of the walls support this idea. The results indicate that oxalic acid concentrations in the early stage of infection stay below the toxic level. In plant and fungi oxalic acid/calcium oxalate plays an important role in calcium regulation. Oxalic acid likely could quench calcium ions released during cell wall breakdown to protect growing hyphae from toxic calcium concentrations in the infection area. As calcium antimonate-precipitates were found in vesicles of young hyphae, we propose that calcium is translocated to the older parts of hyphae and detoxified by building non-toxic, stable oxalate crystals. We propose an infection model where oxalic acid plays a detoxifying role in late infection stages. PMID:23951305

  1. The oxalic acid biosynthetic activity of Burkholderia mallei is encoded by a single locus

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  2. Effect of oxalic acid on Nosema ceranae infection.

    PubMed

    Nanetti, Antonio; Rodriguez-García, Cristina; Meana, Aránzazu; Martín-Hernández, Raquel; Higes, Mariano

    2015-10-01

    Nosema ceranae is a honey bee pathogen parasitizing the ventricular epithelium and potentially causing colony death. The effect of 0.25 M oxalic acid solution administered to the bees in the form of sugar syrup was determined in laboratory and field trials. The spore numbers in an 8-day laboratory experiment were significantly lower when AO was administered (treated: 11.86 ± 0.94 s.e. × 10^6; untreated: 30.64 ± 0.31 s.e.x10^6). When administered in autumn to free flying colonies twice, 3 weeks apart, the infection prevalence decreased in young (relative reduction of 53.8% ± 6.5 s.e.) and old bees (relative reduction of 44.4% ± 6.0 s.e.). Meanwhile increased prevalence in all the controls was detected (young and old bees: relative increase of 45.7% ± 22.8 s.e. and 10.2% ± 5.9 s.e., respectively). While all the treated colonies overwintered correctly, the untreated ones did not (3 out of 5 were dead). In the absence of commercial products approved in several countries to control nosemosis, oxalic acid syrup appears promising in the development of alternative management strategies.

  3. Effect of oxalic acid on Nosema ceranae infection.

    PubMed

    Nanetti, Antonio; Rodriguez-García, Cristina; Meana, Aránzazu; Martín-Hernández, Raquel; Higes, Mariano

    2015-10-01

    Nosema ceranae is a honey bee pathogen parasitizing the ventricular epithelium and potentially causing colony death. The effect of 0.25 M oxalic acid solution administered to the bees in the form of sugar syrup was determined in laboratory and field trials. The spore numbers in an 8-day laboratory experiment were significantly lower when AO was administered (treated: 11.86 ± 0.94 s.e. × 10^6; untreated: 30.64 ± 0.31 s.e.x10^6). When administered in autumn to free flying colonies twice, 3 weeks apart, the infection prevalence decreased in young (relative reduction of 53.8% ± 6.5 s.e.) and old bees (relative reduction of 44.4% ± 6.0 s.e.). Meanwhile increased prevalence in all the controls was detected (young and old bees: relative increase of 45.7% ± 22.8 s.e. and 10.2% ± 5.9 s.e., respectively). While all the treated colonies overwintered correctly, the untreated ones did not (3 out of 5 were dead). In the absence of commercial products approved in several countries to control nosemosis, oxalic acid syrup appears promising in the development of alternative management strategies. PMID:26412538

  4. 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

  5. Synthesis of Oxalic Acid by Enzymes from Lettuce Leaves

    PubMed Central

    Davies, David D.; Asker, Hassan

    1983-01-01

    A rapid purification of lactate dehydrogenase and glycolate oxidase from lettuce (Lactuca sativa) leaves is described. The kinetics of both enzymes are reported in relation to their possible roles in the production of oxalate. Lettuce lactate dehydrogenase behaves like mammalian dehydrogenase, catalyzing the dismutation of glyoxylate to glycolate and oxalate. A model is proposed in which glycolate oxidase in the peroxisomes and lactate dehydrogenase in the cytosol are involved in the production of oxalate. The effect of pH on the balance between oxalate and glycolate produced from glyoxylate suggests that in leaves lactate dehydrogenase may function as part of an oxalate-based biochemical, pH-stat. PMID:16662946

  6. Oxalic acid biosynthesis is encoded by an operon in Burkholderia glumae

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  7. Effect of oxalic acid treatment on sediment arsenic concentrations and lability under reducing conditions.

    PubMed

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

    2016-07-01

    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 treated Dover samples. Therefore, the efficacy of enhanced P&T must consider sediment Fe mineralogy when evaluating its overall potential for remediating groundwater As.

  8. Multifold Increases in Turing Pattern Wavelength in the Chlorine Dioxide-Iodine-Malonic Acid Reaction-Diffusion System

    NASA Astrophysics Data System (ADS)

    Gaskins, Delora K.; Pruc, Emily E.; Epstein, Irving R.; Dolnik, Milos

    2016-07-01

    Turing patterns in the chlorine dioxide-iodine-malonic acid reaction were modified through additions of sodium halide salt solutions. The range of wavelengths obtained is several times larger than in the previously reported literature. Pattern wavelength was observed to significantly increase with sodium bromide or sodium chloride. A transition to a uniform state was found at high halide concentrations. The observed experimental results are qualitatively well reproduced in numerical simulations with the Lengyel-Epstein model with an additional chemically realistic kinetic term to account for the added halide and an adjustment of the activator diffusion rate to allow for interhalogen formation.

  9. Multifold Increases in Turing Pattern Wavelength in the Chlorine Dioxide-Iodine-Malonic Acid Reaction-Diffusion System.

    PubMed

    Gaskins, Delora K; Pruc, Emily E; Epstein, Irving R; Dolnik, Milos

    2016-07-29

    Turing patterns in the chlorine dioxide-iodine-malonic acid reaction were modified through additions of sodium halide salt solutions. The range of wavelengths obtained is several times larger than in the previously reported literature. Pattern wavelength was observed to significantly increase with sodium bromide or sodium chloride. A transition to a uniform state was found at high halide concentrations. The observed experimental results are qualitatively well reproduced in numerical simulations with the Lengyel-Epstein model with an additional chemically realistic kinetic term to account for the added halide and an adjustment of the activator diffusion rate to allow for interhalogen formation. PMID:27517779

  10. EFFECTIVENESS OF USING DILUTE OXALIC ACID TO DISSOLVEHIGH LEVEL WASTE IRON BASED SLUDGE SIMULANT

    SciTech Connect

    Ketusky, E

    2008-07-11

    At the Savannah River Site (SRS), near Aiken South Carolina, there is a crucial need to remove residual quantities of highly radioactive iron-based sludge from large select underground storage tanks (e.g., 19,000 liters of sludge per tank), in order to support tank closure. The use of oxalic acid is planned to dissolve the residual sludge, hence, helping in the removal. Based on rigorous testing, primarily using 4 and 8 wt% oxalic acid solutions, it was concluded that the more concentrated the acid, the greater the amount of residual sludge that would be dissolved; hence, a baseline technology on using 8 wt% oxalic acid was developed. In stark contrast to the baseline technology, reports from other industries suggest that the dissolution will most effectively occur at 1 wt% oxalic acid (i.e., maintaining the pH near 2). The driver for using less oxalic acid is that less (i.e., moles) would decrease the severity of the downstream impacts (i.e., required oxalate solids removal efforts). To determine the initial feasibility of using 1 wt% acid to dissolve > 90% of the sludge solids, about 19,000 liters of representative sludge was modeled using about 530,000 liters of 0 to 8 wt% oxalic acid solutions. With the chemical thermodynamic equilibrium based software results showing that 1 wt% oxalic acid could theoretically work, simulant dissolution testing was initiated. For the dissolution testing, existing simulant was obtained, and an approximate 20 liter test rig was built. Multiple batch dissolutions of both wet and air-dried simulant were performed. Overall, the testing showed that dilute oxalic acid dissolved a greater fraction of the stimulant and resulted in a significantly larger acid effectiveness (i.e., grams of sludge dissolved/mole of acid) than the baseline technology. With the potential effectiveness confirmed via simulant testing, additional testing, including radioactive sludge testing, is planned.

  11. Availability to rats of iron from spinach: Effects of oxalic acid.

    PubMed

    Van Campen, D R; Welch, R M

    1980-08-01

    The availability to rats of iron from two varieties of spinach was determined. Also, the absorption of Fe was compared between FeCl3 and Fe-oxalate and the effects of adding 0.75% oxalate to the diet were determined. Absorption of iron from both varieties of spinach was comparable to that from FeCl3 and the iron was equally available from Fe-oxalate and FeCl3. The addition of 0.75% oxalic acid to the diet did not depress iron absorption and, if anything, appeared to enhance iron utilization by rats.

  12. Determination of trace amount of oxalic acid with zirconium(IV)-(DBS-arsenazo) by spectrophotometry

    NASA Astrophysics Data System (ADS)

    Zhai, Qing-Zhou

    2008-11-01

    A novel method is proposed for the determination of trace amount of oxalic acid in the present article. In 1.0 M hydrochloric acid medium, oxalic acid can react with the zirconium(IV) in Zr(IV)-(DBS-arsenazo) complex and replaces the DBS-arsenazo to produce a hyperchromic effect at 520 nm. The hyperchromic degree is proportional to the concentration of the oxalic acid added over a defined range. Based on this property, a new method for the spectrophotometric determination of trace oxalic acid was developed. Beer's law is held over the concentration range of 9.0 × 10 -6 to 5.0 × 10 -4 M for oxalic acid with a correlation coefficient of 0.9995. The apparent molar absorptivity of the method is ɛ520 nm = 1.16 × 10 3 L mol -1 cm -1 and the detection limit for oxalic acid is 0.815 μg/mL. The developed method was directly applied to the determination of oxalic acid in tomato samples with satisfactory results.

  13. [Catalytic ozonation by ceramic honeycomb for the degradation of oxalic acid in aqueous solution].

    PubMed

    Zhao, Lei; Sun, Zhi-Zhong; Ma, Jun

    2007-11-01

    Comparative experiments for the degradation of oxalic acid in aqueous solution were carried out in the three processes of ozonation alone, ceramic honeycomb-catalyzed ozonation and ceramic honeycomb adsorption. The results show that the degradation rates of oxalic acid in the ceramic honeycomb-catalyzed ozonation, ozonation alone and ceramic honeycomb adsorption systems are 37.6%, 2.2% and 0.4%, and the presence of ceramic honeycomb catalyst significantly improves the degradation rate of oxalic acid compared to the results from non-catalytic ozonation and adsorption. With the addition of tert-butanol, the degradation rates of oxalic acid in catalytic ozonation system decrease by 24.1%, 29.0% and 30.1%, respectively, at the concentration of 5, 10 and 15 mg x L(-1). This phenomenon indicates that ceramic honeycomb-catalyzed ozonation for the degradation of oxalic acid in aqueous solution follows the mechanism of *OH oxidation, namely the heterogeneous surface of catalyst enhances the initiation of *OH. The results of TOC analysis demonstrate that the process of ceramic honeycomb-catalyzed ozonation can achieve the complete mineralization level without the formation of intermediary degradation products. The experimental results suggest that the reaction temperature has positive relationship with the degradation rate of oxalic acid. The degradation rates of oxalic acid in the ceramic honeycomb-catalyzed ozonation system are 16.4%, 37.6%, 61.3% and 68.2%, at the respective reaction temperature of 10, 20, 30 and 40 degrees C.

  14. The origin of free brain malonate

    SciTech Connect

    Riley, K.M.; Dickson, A.C.; Koeppen, A.H. )

    1991-02-01

    Rat brain contains substantial concentrations of free malonate (192 nmol/g wet weight) but origin and biological importance of the dicarboxylic acid are poorly understood. A dietary source has been excluded. A recently described malonyl-CoA decarboxylase deficiency is associated with malonic aciduria and clinical manifestations, including mental retardation. In an effort to study the metabolic origin of free malonate, several labeled acetyl-CoA precursors were administered by intracerebral injection. (2-14C)pyruvate or (1,5-14C)citrate produced radioactive glutamate but failed to label malonate. In contrast, (1-14C)acetate, (2-14C)acetate, and (1-14C)butyrate were converted to labeled glutamate and malonate after the same route of administration. The intracerebral injection of (1-14C)-beta-alanine as a precursor of malonic semialdehyde and possibly free malonate did not give rise to radioactivity in the dicarboxylate. The labeling pattern of malonic acid is compatible with the reaction sequence: acetyl-CoA----malonyl-CoA----malonate. The final step is thought to occur by transfer of the CoA-group from malonyl-CoA to succinate and/or acetoacetate. Labeling of malonate from acetate is most effective at the age of 7 days when the net concentration of the dicarboxylic acid in rat brain is still very low. At this age, butyrate was a better precursor of malonate than acetate. It is proposed that fatty acid oxidation provides the acetyl-CoA which functions as the precursor of free brain malonate. Compartmentation of malonate biosynthesis is likely because the acetyl-CoA precursors citrate and pyruvate are ineffective.

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

    PubMed

    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.

  16. 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

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

    PubMed

    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

  18. The influence of dicarboxylic acids: Oxalic acid and tartaric acid on the compressive strength of glass ionomer cements

    NASA Astrophysics Data System (ADS)

    Permana, Ahmadi Jaya; Setyawati, Harsasi; Hamami, Murwani, Irmina Kris

    2016-03-01

    Glass ionomer cement (GIC) has limitation on the mechanical properties especially compressive strength. The change of compressive strength of GIC by adding oxalic acid and tartaric acid has been investigated. Oxalic acid and tartaric acid was added to the liquid components at concentrations of 0 - 15% (w/w). Powder component of GIC was made from optimum experimental powder glass SiO2-Al2O3-CaF2. GIC was characterized by compressive strength test, SEM-EDX and FTIR. The addition of tartaric acid to GIC has greater improvement than addition of oxalic acid. The addition of tartaric acid at 10 % (w/w) to GIC has greatest value of compressive strength.

  19. Acute renal failure and metabolic acidosis due to oxalic acid intoxication: a case report.

    PubMed

    Yamamoto, Rie; Morita, Seiji; Aoki, Hiromichi; Nakagawa, Yoshihide; Yamamoto, Isotoshi; Inokuchi, Sadaki

    2011-12-01

    Most of the reports of oxalic acid intoxication are in cases of ethylene glycol intoxication. These symptoms are known to be central nerve system manifestations, cardiopulmonary manifestations and acute renal failure. There have been only a few reports of direct oxalic acid intoxication. However, there have been a few recent reports of oxalic acid intoxication due to the ingestion of star fruit and ascorbic acid. We herein report the case of a patient with acute renal failure and metabolic acidosis caused directly by consumption of oxalic acid. During the initial examination by the physician at our hospital, the patient presented with tachypnea, a precordinal burning sensation, nausea and metabolic acidosis. After admission, the patient developed renal failure and anion gap high metabolic acidosis, but did not develop any CNS or cardio-pulmonary manifestations in the clinical course. The patient benefitted symptomatically from hemodialysis.

  20. Crystallization and immersion freezing ability of oxalic and succinic acid in multicomponent aqueous organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Wagner, Robert; Höhler, Kristina; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin

    2015-04-01

    This study reports on heterogeneous ice nucleation efficiency of immersed oxalic and succinic acid crystals in the temperature range from 245 to 215 K, as investigated with expansion cooling experiments using suspended particles. In contrast to previous laboratory work with emulsified solution droplets where the precipitation of solid inclusions required a preceding freezing/evaporation cycle, we show that immersed solids readily form by homogeneous crystallization within aqueous solution droplets of multicomponent organic mixtures, which have noneutonic compositions with an excess of oxalic or succinic acid. Whereas succinic acid crystals did not act as heterogeneous ice nuclei, immersion freezing by oxalic acid dihydrate crystals led to a reduction of the ice saturation ratio at freezing onset by 0.066-0.072 compared to homogeneous freezing, which is by a factor of 2 higher than previously reported laboratory data. These observations emphasize the importance of oxalic acid in heterogeneous ice nucleation.

  1. Role of Oxalic Acid Overexcretion in Transformations of Toxic Metal Minerals by Beauveria caledonica

    PubMed Central

    Fomina, M.; Hillier, S.; Charnock, J. M.; Melville, K.; Alexander, I. J.; Gadd, G. M.

    2005-01-01

    The fungus Beauveria caledonica was highly tolerant to toxic metals and solubilized cadmium, copper, lead, and zinc minerals, converting them into oxalates. This fungus was found to overexcrete organic acids with strong metal-chelating properties (oxalic and citric acids), suggesting that a ligand-promoted mechanism was the main mechanism of mineral dissolution. Our data also suggested that oxalic acid was the main mineral-transforming agent. Cadmium, copper, and zinc oxalates were precipitated by the fungus in the local environment and also in association with the mycelium. The presence of toxic metal minerals often led to the formation of mycelial cords, and in the presence of copper-containing minerals, these cords exhibited enhanced excretion of oxalic acid, which resulted in considerable encrustation of the cords by copper oxalate hydrate (moolooite). It was found that B. caledonica hyphae and cords were covered by a thick hydrated mucilaginous sheath which provided a microenvironment for chemical reactions, crystal deposition, and growth. Cryo-scanning electron microscopy revealed that mycogenic metal oxalates overgrew parental fungal hyphae, leaving a labyrinth of fungal tunnels within the newly formed mineral matter. X-ray absorption spectroscopy revealed that oxygen ligands played a major role in metal coordination within the fungal biomass during the accumulation of mobilized toxic metals by B. caledonica mycelium; these ligands were carboxylic groups in copper phosphate-containing medium and phosphate groups in pyromorphite-containing medium. PMID:15640211

  2. A biogenic source of oxalic acid and glyoxal in marine boundary layer

    NASA Astrophysics Data System (ADS)

    Facchini, C.; Rinaldi, M.; Ceburnis, D.; O'Dowd, C.; Sciare, J.; Burrows, J. P.

    2011-12-01

    We present the results of oxalic acid aerosol measurements samples performed at Mace Head (Ireland, 53°20'N, 9°54'W) and Amsterdam Island (Indian Ocean, 37°48'S, 77°34'E), supporting the existence of a biogenic source of oxalic acid over the oceans. Aerosol oxalic acid was detected in clean marine air masses in concentrations ranging from 2.7 to 39 ng m-3, at Mace Head, and from 0.31 to 17 ng m-3, at Amsterdam Island. In both hemispheres, oxalic acid concentration showed a clear seasonal trend, with maxima in spring-summer and minima in the fall-winter period, in analogy with other marine biogenic aerosol components (e.g., MSA and amines). Oxalic acid was distributed along the whole aerosol size spectrum, with the major contribution given by the 1.0-2.0 μm size range, and by the lower accumulation mode (0.25-0.5 μm). Given the observed size distributions, marine aerosol oxalic acid can be assumed as the result of the combination of different formation processes, among which in-cloud oxidation of gaseous precursors [1] and photochemical degradation of biogenic unsaturated fatty acids [2] are likely the most important. Among aerosol oxalic acid precursors, glyoxal is the most likely candidate in the marine boundary layer, as a source of glyoxal over the oceans has recently been discovered by satellite observations [3] and confirmed by in situ measurements [4]. In support of this hypothesis, SCIAMACHY satellite retrieved glyoxal column concentrations, over the two sampling sites, resulted characterized by a clear seasonal trend, resembling the aerosol oxalic acid one. [1] Warneck, Atmospheric Environment, 37, 2423-2427, 2003. [2] Kawamura & Sakaguchi, J. Geophys. Res., 104, D3, 3501-3509, 1999. [3] Fu et al., J. Geophys. Res., 113, D15303, doi:10.1029/2007JD009505, 2008 [4] Sinreich et al., Atmos. Chem. Phys. Discuss., 10, 15075-15107, 2010.

  3. Malonic acid concentration as a control parameter in the kinetic analysis of the Belousov-Zhabotinsky reaction under batch conditions.

    PubMed

    Blagojević, Slavica M; Anić, Slobodan R; Cupić, Zeljko D; Pejić, Natasa D; Kolar-Anić, Ljiljana Z

    2008-11-28

    The influence of the initial malonic acid concentration [MA]0 (8.00 x 10(-3) < or = [MA]0 < or = 4.30 x 10(-2) mol dm(-3)) in the presence of bromate (6.20 x 10(-2) mol dm(-3)), bromide (1.50 x 10(-5) mol dm(-3)), sulfuric acid (1.00 mol dm(-3)) and cerium sulfate (2.50 x 10(-3) mol dm(-3)) on the dynamics and the kinetics of the Belousov-Zhabotinsky (BZ) reactions was examined under batch conditions at 30.0 degrees C. The kinetics of the BZ reaction was analyzed by the earlier proposed method convenient for the examinations of the oscillatory reactions. In the defined region of parameters where oscillograms with only large-amplitude relaxation oscillations appeared, the pseudo-first order of the overall malonic acid decomposition with a corresponding rate constant of 2.14 x 10(-2) min(-1) was established. The numerical results on the dynamics and kinetics of the BZ reaction, carried out by the known skeleton model including the Br2O species, were in good agreement with the experimental ones. The already found saddle node infinite period (SNIPER) bifurcation point in transition from a stable quasi-steady state to periodic orbits and vice versa is confirmed by both experimental and numerical investigations of the system under consideration. Namely, the large-amplitude relaxation oscillations with increasing periods between oscillations in approaching the bifurcation points at the beginning and the end of the oscillatory domain, together with excitability of the stable quasi-steady states in their vicinity are obtained.

  4. Production of citric and oxalic acids and solubilization of calcium phosphate by Penicillium bilaii.

    PubMed Central

    Cunningham, J E; Kuiack, C

    1992-01-01

    An isolate of Penicillium bilaii previously reported to solubilize mineral phosphates and enhance plant uptake of phosphate was studied. Using agar media with calcium phosphate and the pH indicator alizarin red S, the influence of the medium composition on phosphate solubility and medium acidification was recorded. The major acidic metabolites produced by P. bilaii in a sucrose nitrate liquid medium were found to be oxalic acid and citric acid. Citric acid production was promoted under nitrogen-limited conditions, while oxalic acid production was promoted under carbon-limited conditions. Citric acid was produced in both growth and stationary phases, but oxalic acid production occurred only in stationary phase. When submerged cultures which normally produce acid were induced to sporulate, the culture medium shifted toward alkaline rather than acid reaction with growth. PMID:1622211

  5. Determination of water-soluble forms of oxalic and formic acids in soils by ion chromatography

    NASA Astrophysics Data System (ADS)

    Karicheva, E.; Guseva, N.; Kambalina, M.

    2016-03-01

    Carboxylic acids (CA) play an important role in the chemical composition origin of soils and migration of elements. The content of these acids and their salts is one of the important characteristics for agrochemical, ecological, ameliorative and hygienic assessment of soils. The aim of the article is to determine water-soluble forms of same carboxylic acids — (oxalic and formic acids) in soils by ion chromatography with gradient elution. For the separation and determination of water-soluble carboxylic acids we used reagent-free gradient elution ion-exchange chromatography ICS-2000 (Dionex, USA), the model solutions of oxalate and formate ions, and leachates from soils of the Kola Peninsula. The optimal gradient program was established for separation and detection of oxalate and formate ions in water solutions by ion chromatography. A stability indicating method was developed for the simultaneous determination of water-soluble organic acids in soils. The method has shown high detection limits such as 0.03 mg/L for oxalate ion and 0.02 mg/L for formate ion. High signal reproducibility was achieved in wide range of intensities which correspond to the following ion concentrations: from 0.04 mg/g to 10 mg/L (formate), from 0.1 mg/g to 25 mg/L (oxalate). The concentration of formate and oxalate ions in soil samples is from 0.04 to 0.9 mg/L and 0.45 to 17 mg/L respectively.

  6. Enolate Stabilization by Anion-π Interactions: Deuterium Exchange in Malonate Dilactones on π-Acidic Surfaces.

    PubMed

    Miros, François N; Zhao, Yingjie; Sargsyan, Gevorg; Pupier, Marion; Besnard, Céline; Beuchat, César; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2016-02-18

    Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion-π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π-acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π-acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α-protons in the (1) H NMR spectra. The reactivity of these protons on π-acidic surfaces is measured by hydrogen-deuterium (H-D) exchange for 11 different examples, excluding controls. The velocity of H-D exchange increases with π acidity (NDI core substituents: SO2 R>SOR>H>OR>OR/NR2 >SR>NR2 ). The H-D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11-13 atoms). Most importantly, H-D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure (R,R,P)-macrocycle is reported). For maximal π acidity, transition-state stabilizations up to -18.8 kJ mol(-1) are obtained for H-D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured pKa =10.9 calculates to a ΔpKa =-5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as "impossible" in biology, the found enolate-π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven-component π-acidity gradient over almost 1 eV demonstrates quantitatively that such important anion-π activities can be expected only from

  7. Acetate induced enhancement of photocatalytic hydrogen peroxide production from oxalic acid and dioxygen.

    PubMed

    Yamada, Yusuke; Nomura, Akifumi; Miyahigashi, Takamitsu; Ohkubo, Kei; Fukuzumi, Shunichi

    2013-05-01

    The addition of acetate ion to an O2-saturated mixed solution of acetonitrile and water containing oxalic acid as a reductant and 2-phenyl-4-(1-naphthyl)quinolinium ion (QuPh(+)-NA) as a photocatalyst dramatically enhanced the turnover number of hydrogen peroxide (H2O2) production. In this photocatalytic H2O2 production, a base is required to facilitate deprotonation of oxalic acid forming oxalate dianion, which acts as an actual electron donor, whereas a Brønsted acid is also necessary to protonate O2(•-) for production of H2O2 by disproportionation. The addition of acetate ion to a reaction solution facilitates both the deprotonation of oxalic acid and the protonation of O2(•-) owing to a pH buffer effect. The quantum yield of the photocatalytic H2O2 production under photoirradiation (λ = 334 nm) of an O2-saturated acetonitrile-water mixed solution containing acetate ion, oxalic acid and QuPh(+)-NA was determined to be as high as 0.34, which is more than double the quantum yield obtained by using oxalate salt as an electron donor without acetate ion (0.14). In addition, the turnover number of QuPh(+)-NA reached more than 340. The reaction mechanism and the effect of solvent composition on the photocatalytic H2O2 production were scrutinized by using nanosecond laser flash photolysis.

  8. REMOVING SLUDGE HEELS FROM SAVANNAH RIVER SITE WASTE TANKS BY OXALIC ACID DISSOLUTION

    SciTech Connect

    Poirier, M; David Herman, D; Fernando Fondeur, F; John Pareizs, J; Michael Hay, M; Bruce Wiersma, B; Kim Crapse, K; Thomas Peters, T; Samuel Fink, S; Donald Thaxton, D

    2009-03-01

    The Savannah River Site (SRS) will remove sludge as part of waste tank closure operations. Typically the bulk sludge is removed by mixing it with supernate to produce a slurry, and transporting the slurry to a downstream tank for processing. Experience shows that a residual heel may remain in the tank that cannot be removed by this conventional technique. In the past, SRS used oxalic acid solutions to disperse or dissolve the sludge heel to complete the waste removal. To better understand the actual conditions of oxalic acid cleaning of waste from carbon steel tanks, the authors developed and conducted an experimental program to determine its effectiveness in dissolving sludge, the hydrogen generation rate, the generation rate of other gases, the carbon steel corrosion rate, the impact of mixing on chemical cleaning, the impact of temperature, and the types of precipitates formed during the neutralization process. The test samples included actual SRS sludge and simulated SRS sludge. The authors performed the simulated waste tests at 25, 50, and 75 C by adding 8 wt % oxalic acid to the sludge over seven days. They conducted the actual waste tests at 50 and 75 C by adding 8 wt % oxalic acid to the sludge as a single batch. Following the testing, SRS conducted chemical cleaning with oxalic acid in two waste tanks. In Tank 5F, the oxalic acid (8 wt %) addition occurred over seven days, followed by inhibited water to ensure the tank contained enough liquid to operate the mixer pumps. The tank temperature during oxalic acid addition and dissolution was approximately 45 C. The authors analyzed samples from the chemical cleaning process and compared it with test data. The conclusions from the work are: (1) Oxalic acid addition proved effective in dissolving sludge heels in the simulant demonstration, the actual waste demonstration, and in SRS Tank 5F. (2) The oxalic acid dissolved {approx} 100% of the uranium, {approx} 100% of the iron, and {approx} 40% of the manganese

  9. Solubilities and Glass Formation in Aqueous Solutions of the Sodium Salts of Malonic Acid With and Without Ammonium Sulfate.

    PubMed

    Kissinger, Jared A; Buttke, Lukas G; Vinokur, Anastasiya I; Guzei, Ilia A; Beyer, Keith D

    2016-06-01

    The solubility of sodium hydrogen malonate and sodium malonate in water both with and without ammonium sulfate present has been studied using differential scanning calorimetry and infrared spectroscopy. The crystals that form from sodium hydrogen malonate/water solutions were determined to be sodium hydrogen malonate monohydrate by single-crystal X-ray diffractometry. The crystals formed in sodium malonate/water solutions were determined to be sodium malonate monohydrate, a compound whose structure had not been previously known. When ammonium sulfate is added to these respective aqueous systems, the precipitation solids contain sodium sulfate decahydrate under low to moderate ammonium concentrations and lecontite (NaNH4SO4·2H2O) under high ammonium concentrations, which can be found under dry atmospheric conditions. Thus, it appears the presence of malonate and hydrogen malonate ions does not significantly affect the precipitation of inorganic salts in these systems. The glass transition temperatures of all solutions were also determined, and it was observed that the addition of ammonium sulfate slightly lowers the glass transition temperature in these solutions.

  10. 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. PMID:27258452

  11. 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

  12. 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.

  13. 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.

  14. Corrosion Behavior of Alloy 22 in Oxalic Acid and Sodium Chloride Solutions

    SciTech Connect

    Day, S D; Whalen, M T; King, K J; Hust, G A; Wong, L L; Estill, J C; Rebak, R B

    2003-06-24

    Nickel based Alloy 22 (NO6022) is extensively used in aggressive industrial applications, especially due to its resistance to localized corrosion and stress corrosion cracking in high chloride environments. The purpose of this work was to characterize the anodic behavior of Alloy 22 in oxalic acid solution and to compare its behavior to sodium chloride (NaCl) solutions. Standard electrochemical tests such as polarization resistance and cyclic polarization were used. Results show that the corrosion rate of Alloy 22 in oxalic acid solutions increased rapidly as the temperature and the acid concentration increased. Extrapolation studies show that even at a concentration of 10{sup -4}M oxalic acid, the corrosion rate of Alloy 22 would be higher in oxalic acid than in 1 M NaCl solution. Alloy 22 was not susceptible to localized corrosion in oxalic acid solutions. Cyclic polarization tests in 1 M NaCl showed that Alloy 22 was susceptible to crevice corrosion at 90 C but was not susceptible at 60 C.

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

    SciTech Connect

    Peng, Xiu-Qiu; Liu, Yi-Rong; Huang, Teng; Jiang, Shuai; Huang, Wei

    2015-04-14

    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 the 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.

  16. Ferromagnetic coupling in the three-dimensional malonato-bridged gadoliniumIII complex [Gd2(mal)3(H2O)6] (H2mal = malonic acid).

    PubMed

    Hernández-Molina, María; Ruiz-Pérez, Catalina; López, Trinidad; Lloret, Francesc; Julve, Miguel

    2003-09-01

    The novel gadolinium(III) complex of formula [Gd(2)(mal)(3)(H(2)O)(6)] (1) (H(2)mal = 1,3-propanedioic acid) has been prepared and characterized by X-ray diffraction analysis. Crystal data for 1: monoclinic, space group I2/a, a = 11.1064(10) A, b = 12.2524(10) A, c =13.6098(2) A, beta = 92.925(10) degrees, U = 1849.5(3) A(3), Z = 4. Compound 1 is a three-dimensional network made up of malonate-bridged gadolinium(III) ions where the malonate exhibits two bridging modes, eta(5)-bidentate + unidentate and eta(3):eta(3) + bis(unidentate). The gadolinium atom is nine-coordinate with three water molecules and six malonate oxygen atoms from three malonate ligands forming a distorted monocapped square antiprism. The shortest metal-metal separations are 4.2763(3) A [through the oxo-carboxylate bridge] and 6.541(3) A [through the carboxylate in the anti-syn coordination mode]. The value of the angle at the oxo-carboxylate atom is 116.8(2) degrees. Variable-temperature magnetic susceptibility measurements reveal the occurrence of a significant ferromagnetic interaction through the oxo-carboxylate pathway (J = +0.048(1) cm(-1), H = -JS(Gd(1)) x S(Gd(1a))).

  17. Fungal production of citric and oxalic acid: importance in metal speciation, physiology and biogeochemical processes.

    PubMed

    Gadd, G M

    1999-01-01

    The production of organic acids by fungi has profound implications for metal speciation, physiology and biogeochemical cycles. Biosynthesis of oxalic acid from glucose occurs by hydrolysis of oxaloacetate to oxalate and acetate catalysed by cytosolic oxaloacetase, whereas on citric acid, oxalate production occurs by means of glyoxylate oxidation. Citric acid is an intermediate in the tricarboxylic acid cycle, with metals greatly influencing biosynthesis: growth limiting concentrations of Mn, Fe and Zn are important for high yields. The metal-complexing properties of these organic acids assist both essential metal and anionic (e.g. phosphate) nutrition of fungi, other microbes and plants, and determine metal speciation and mobility in the environment, including transfer between terrestrial and aquatic habitats, biocorrosion and weathering. Metal solubilization processes are also of potential for metal recovery and reclamation from contaminated solid wastes, soils and low-grade ores. Such 'heterotrophic leaching' can occur by several mechanisms but organic acids occupy a central position in the overall process, supplying both protons and a metal-complexing organic acid anion. Most simple metal oxalates [except those of alkali metals, Fe(III) and Al] are sparingly soluble and precipitate as crystalline or amorphous solids. Calcium oxalate is the most important manifestation of this in the environment and, in a variety of crystalline structures, is ubiquitously associated with free-living, plant symbiotic and pathogenic fungi. The main forms are the monohydrate (whewellite) and the dihydrate (weddelite) and their formation is of significance in biomineralization, since they affect nutritional heterogeneity in soil, especially Ca, P, K and Al cycling. The formation of insoluble toxic metal oxalates, e.g. of Cu, may confer tolerance and ensure survival in contaminated environments. In semi-arid environments, calcium oxalate formation is important in the formation and

  18. The effect of oxalic and itaconic acids on threo-Ds-isocitric acid production from rapeseed oil by Yarrowia lipolytica.

    PubMed

    Kamzolova, Svetlana V; Allayarov, Ramil K; Lunina, Julia N; Morgunov, Igor G

    2016-04-01

    The effect of oxalic and itaconic acids, the inhibitors of the isocitrate lyase, on the production of isocitric acid by the wild strain Yarrowia lipolytica VKM Y-2373 grown in the medium containing rapeseed oil was studied. In the presence of oxalic and itaconic acids, strain Y. lipolytica accumulated in the medium isocitric acid (70.0 and 82.7 g/L, respectively) and citric acid (23.0 and 18.4 g/L, respectively). In control experiment, when the inhibitors were not added to the medium, the strain accumulated isocitric and citric acids at concentrations of 62.0 and 28.0 g/L, respectively. Thus, the use of the oxalic and itaconic acids as additives to the medium is a simple and convenient method of isocitric acid production with a minimum content of citric acid.

  19. The adsorption and photo-degradation of oxalic acid at the TiO2 surface.

    NASA Astrophysics Data System (ADS)

    Mendive, Cecilia; Blesa, Miguel; Bahnemann, Detlef

    2006-03-01

    Oxalic acid is the simplest model compound to study the heterogeneous photocatalytic oxidation of pollutants on TiO2 containing more than one carboxylate group. We have carried out a study of a system of an oxalic acid solution in contact with a thin film of TiO2 particles employing ATR - FTIR in combination with quantum chemical calculations. Thus, possible adsorption structures have been identified and molecular dynamic simulations have been used to compare their predictions with the experimental data. It was found that the adsorption of oxalic acid on TiO2 in the dark can be explained in terms of two surface complexation modes for the anatase phase and only one surface complexation mode for the rutile phase. We have found that under illumination one of the complexes on the anatase phase preferably undergoes photo-degradation. At the same time water molecules are desorbed from the TiO2 surface by a thermal mechanism induced by the absorption of photons. Both processes favor the adsorption of more molecules of oxalic acid at the TiO2 surface which is thus enriched in the second complexation mode. A similar mechanism was found to occur on the rutile phase. The only complexation mode appears not to be photo-sensitive but the TiO2 surface is enriched in oxalic acid under illumination due to the replacement of photo-desorbed water molecules.

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

    SciTech Connect

    STALLINGS, MARY

    2004-07-08

    This report presents findings from tests investigating the dissolution of simulated and radioactive Savannah River Site sludges with 4 per cent oxalic acid and mixtures of oxalic and citric acid previously recommended by a Russian team from the Khlopin Radium Institute and the Mining and Chemical Combine (MCC). Testing also included characterization of the simulated and radioactive waste sludges. Testing results showed the following: Dissolution of simulated HM and PUREX sludges with oxalic and citric acid mixtures at SRTC confirmed general trends reported previously by Russian testing. Unlike the previous Russian testing six sequential contacts of a mixture of oxalic acid citric acids at a 2:1 ratio (v/w) of acid to sludge did not produce complete dissolution of simulated HM and PUREX sludges. We observed that increased sludge dissolution occurred at a higher acid to sludge ratio, 50:1 (v/w), compared to the recommended ratio of 2:1 (v/w). We observed much lower dissolution of aluminum in a simulated HM sludge by sodium hydroxide leaching. We attribute the low aluminum dissolution in caustic to the high fraction of boehmite present in the simulated sludge. Dissolution of HLW sludges with 4 per cent oxalic acid and oxalic/citric acid followed general trends observed with simulated sludges. The limited testing suggests that a mixture of oxalic and citric acids is more efficient for dissolving HM and PUREX sludges and provides a more homogeneous dissolution of HM sludge than oxalic acid alone. Dissolution of HLW sludges in oxalic and oxalic/citric acid mixtures produced residual sludge solids that measured at higher neutron poison to equivalent 235U weight ratios than that in the untreated sludge solids. This finding suggests that residual solids do not present an increased nuclear criticality safety risk. Generally the neutron poison to equivalent 235U weight ratios of the acid solutions containing dissolved sludge components are lower than those in the untreated

  1. Iron dissolution of dust source materials during simulated acidic processing: the effect of sulfuric, acetic, and oxalic acids.

    PubMed

    Chen, Haihan; Grassian, Vicki H

    2013-09-17

    Atmospheric organic acids potentially display different capacities in iron (Fe) mobilization from atmospheric dust compared with inorganic acids, but few measurements have been made on this comparison. We report here a laboratory investigation of Fe mobilization of coal fly ash, a representative Fe-containing anthropogenic aerosol, and Arizona test dust, a reference source material for mineral dust, in pH 2 sulfuric acid, acetic acid, and oxalic acid, respectively. The effects of pH and solar radiation on Fe dissolution have also been explored. The relative capacities of these three acids in Fe dissolution are in the order of oxalic acid > sulfuric acid > acetic acid. Oxalate forms mononuclear bidentate ligand with surface Fe and promotes Fe dissolution to the greatest extent. Photolysis of Fe-oxalate complexes further enhances Fe dissolution with the concomitant degradation of oxalate. These results suggest that ligand-promoted dissolution of Fe may play a more significant role in mobilizing Fe from atmospheric dust compared with proton-assisted processing. The role of atmospheric organic acids should be taken into account in global-biogeochemical modeling to better access dissolved atmospheric Fe deposition flux at the ocean surface.

  2. SAVANNAH RIVER SITE TANK CLEANING: CORROSION RATE FOR ONE VERSUS EIGHT PERCENT OXALIC ACID SOLUTION

    SciTech Connect

    Ketusky, E.; Subramanian, K.

    2011-01-20

    Until recently, the use of oxalic acid for chemically cleaning the Savannah River Site (SRS) radioactive waste tanks focused on using concentrated 4 and 8-wt% solutions. Recent testing and research on applicable dissolution mechanisms have concluded that under appropriate conditions, dilute solutions of oxalic acid (i.e., 1-wt%) may be more effective. Based on the need to maximize cleaning effectiveness, coupled with the need to minimize downstream impacts, SRS is now developing plans for using a 1-wt% oxalic acid solution. A technology gap associated with using a 1-wt% oxalic acid solution was a dearth of suitable corrosion data. Assuming oxalic acid's passivation of carbon steel was proportional to the free oxalate concentration, the general corrosion rate (CR) from a 1-wt% solution may not be bound by those from 8-wt%. Therefore, after developing the test strategy and plan, the corrosion testing was performed. Starting with the envisioned process specific baseline solvent, a 1-wt% oxalic acid solution, with sludge (limited to Purex type sludge-simulant for this initial effort) at 75 C and agitated, the corrosion rate (CR) was determined from the measured weight loss of the exposed coupon. Environmental variations tested were: (a) Inclusion of sludge in the test vessel or assuming a pure oxalic acid solution; (b) acid solution temperature maintained at 75 or 45 C; and (c) agitation of the acid solution or stagnant. Application of select electrochemical testing (EC) explored the impact of each variation on the passivation mechanisms and confirmed the CR. The 1-wt% results were then compared to those from the 8-wt%. The immersion coupons showed that the maximum time averaged CR for a 1-wt% solution with sludge was less than 25-mils/yr for all conditions. For an agitated 8-wt% solution with sludge, the maximum time averaged CR was about 30-mils/yr at 50 C, and 86-mils/yr at 75 C. Both the 1-wt% and the 8-wt% testing demonstrated that if the sludge was removed from

  3. On the factors governing the abundance of oxalic acid in tropospheric aerosol particles

    NASA Astrophysics Data System (ADS)

    van Pinxteren, D.; Neusuess, C.; Brüggemann, E.; Gnauk, T.; Müller, K.; Herrmann, H.

    2010-12-01

    Oxalic acid is frequently observed as one of the most abundant single organic compounds in tropospheric particles. Its sources are commonly believed to be of secondary nature. In state-of-the-art multiphase chemistry models, different pathways exist, which can lead to oxalic acid as final product. Anthropogenic hydrocarbon emissions can be photochemically degraded to glyoxal and methyglyoxal, which - after partitioning into deliquescent particles or cloud droplets - are further oxidized via glyoxylic acid to oxalic acid [Herrmann et al., 2005]. A biogenic oxidation pathway starts with isoprene or monoterpene emissions and leads to glycolaldehyde and methylglyoxal via methacrolein and methylvinylketone, followed by aqueous phase oxalic acid formation [Lim et al., 2005]. As suggested by Warneck, 2003, a marine pathway might exist, starting from marine ethene emissions and leading via glycolaldehyde to oxalic acid. The aim of this study was to elucidate from field measurements the importance of each of these pathways. To this aim, oxalic acid concentrations from 144 size-resolved particle samples (5-stage Berner impactor) from different continental and coastal European sampling sites were statistically analyzed using principal component analysis (PCA). Hourly back trajectories were calculated for each sampling interval using the HYSPLIT model [Draxler and Rolph, 2003] and combined in a novel way with global land cover data to yield “residence times” of the sampled air masses above urban, agricultural, forested, and oceanic areas. These residence times served as quantitative proxies for different emission regimes (anthropogenic, biogenic, marine) in the statistical analysis. Additionally, meteorological parameters such as sunflux along the trajectories or mixing layer depth at the sampling site were retrieved from the HYSPLIT output. PCA of the continental dataset retrieved two factors that were connected to the oxalic acid concentrations. A first one showed high

  4. Electrochemical Oxidation and Determination of Oxalic Acid at an Exfoliated Graphite-Polystyrene Composite Electrode

    PubMed Central

    Manea, Florica; Radovan, Ciprian; Corb, Ioana; Pop, Aniela; Burtica, Georgeta; Malchev, Plamen; Picken, Stephen; Schoonman, Joop

    2007-01-01

    An exfoliated graphite-polystyrene composite electrode was evaluated as an alternative electrode in the oxidation and the determination of oxalic acid in 0.1 M Na2SO4 supporting electrolyte. Using CV, LSV, CA procedures, linear dependences I vs. C were obtained in the concentrations range of oxalic acid between 0.5 to 3 mM, with LOD =0.05 mM, and recovery degree of 98%, without need of surface renewing between successive runs. The accuracy of the methods was evaluated as excellent comparing the detection results with that obtained using conventional KMnO4 titration method. In addition, the apparent diffusion coefficient of oxalic acid D was found to be around 2.89 · 10-8 cm2·s-1 by CA and CV.

  5. Condensation of anhydrides or dicarboxylic acids with compounds containing active methylene groups. Part 1: Condensation of phthalic anhydride with acetoacetic and malonic ester

    NASA Technical Reports Server (NTRS)

    Oshkaya, V. P.; Vanag, G. Y.

    1985-01-01

    Phthalic anhydride was condensed with acetoacetic ester in acetic anhydride and triethylamine solution, and when phthalyl chloride was reacted with sodium acetoacetic ester compounds were formed of the phthalide and indandione series: phthalylacetoacetic ester and a derivative of indan-1,3-dione which after boiling with hydrochloric acid yielded indan-1,3-dione. Phthalylmalonic ester was obtained from phthalic anhydride and malonic ester in the presence of triethylamine.

  6. Water adsorption around oxalic acid aggregates: a molecular dynamics simulation of water nucleation on organic aerosols.

    PubMed

    Darvas, Maria; Picaud, Sylvain; Jedlovszky, Pál

    2011-11-28

    The phase behaviour of binary oxalic acid-water mixtures has been investigated by means of computer simulation techniques. Such mixtures play an important role in atmospheric processes, since the hydrogen bonding ability of oxalic acid molecules allows them to form aerosol particles. Water can in turn be readily adsorbed on the surface of such aerosol particles, which results in the formation of small ice grains. These grains are thus considered to be acting as cloud condensation nuclei, giving rise to the formation of ice clouds.

  7. In Situ Investigation of a Self-Accelerated Cocrystal Formation by Grinding Pyrazinamide with Oxalic Acid.

    PubMed

    Kulla, Hannes; Greiser, Sebastian; Benemann, Sigrid; Rademann, Klaus; Emmerling, Franziska

    2016-01-01

    A new cocrystal of pyrazinamide with oxalic acid was prepared mechanochemically and characterized by PXRD, Raman spectroscopy, solid-state NMR spectroscopy, DTA-TG, and SEM. Based on powder X-ray diffraction data the structure was solved. The formation pathway of the reaction was studied in situ using combined synchrotron PXRD and Raman spectroscopy. Using oxalic acid dihydrate the initially neat grinding turned into a rapid self-accelerated liquid-assisted grinding process by the release of crystallization water. Under these conditions, the cocrystal was formed directly within two minutes. PMID:27428942

  8. 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.

  9. Adsorption and stability of malonic acid on rutile TiO2 (110), studied by near edge X-ray absorption fine structure and photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Syres, Karen L.; Thomas, Andrew G.; Graham, Darren M.; Spencer, Ben F.; Flavell, Wendy R.; Jackman, Mark J.; Dhanak, Vinod R.

    2014-08-01

    The adsorption of malonic acid on rutile TiO2 (110) has been studied using photoelectron spectroscopy and C K-edge, near edge X-ray fine structure spectroscopy (NEXAFS). Analysis of the O 1s and Ti 2p spectra suggest that the molecule adsorbs dissociatively in a doubly-bidentate adsorption geometry as malonate. The data are unable to distinguish between a chelating bonding mode with the backbone of the molecule lying along the [001] azimuth or a bridging geometry along the direction. Work carried out on a wiggler beamline suggests that the molecule is unstable under irradiation by high-flux synchrotron radiation from this type of insertion device.

  10. Two new antioxidant malonated caffeoylquinic acid isomers in fruits of wild eggplant relatives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fruits of both the cultivated eggplant species Solanum melongena and its wild relative Solanum incanum have a high content of hydroxycinnamic acid conjugates, which along with other phenylpropanoids are implicated in the human health benefits of various fruits and vegetables. Monocaffeoylquinic acid...

  11. A feasibility study on the multistage process for the oxalic acid pretreatment of a lignocellulosic biomass using electrodialysis.

    PubMed

    Lee, Hong-Joo; Ahn, Sung Ju; Seo, Young-Jun; Lee, Jae-Won

    2013-02-01

    The present study investigated the feasibility of the recovery and reuse oxalic acid in a multistage process for the pretreatment of a lignocellulosic biomass. Electrodialysis (ED), an electrochemical process using ion exchange membranes, was used to recover and reuse oxalic acid in the multistage process. The ED optimal condition for recover oxalic acid was potential of 10V and pH 2.2 in synthetic solutions. The recovery efficiency of oxalic acid from hydrolysates reached 100% at potential of 10V. The power consumption to treat 1mol of oxalic acid was estimated to be 41.0wh. At the same time, ethanol production increased up to 19g/L in the ED-treated hydrolysate, corresponding to ethanol productivity of 0.27g/L/h. It was clearly shown that bioethanol fermentation efficiency increased using the ED process, due to a small loss of fermentable sugar and a significantly high removal of inhibitory chemicals. PMID:23306131

  12. Response to oxalic acid as a resistance assay for Sclerotinia minor in peanut

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Response to oxalic acid was evaluated as a potential assay for screening peanut breeding lines for resistance to Sclerotinia blight caused by Sclerotinia minor. Detached stems of seven Spanish- and six runner-type peanut cultivars and advanced breeding lines, varying in resistance to Sclerotinia bl...

  13. [Catalytic ozonation of oxalic acid in water with Pt/graphite catalyst].

    PubMed

    Liu, Zheng-Qian; Ma, Jun; Zhao, Lei

    2007-06-01

    Pt/graphite catalyst was prepared by incipient wetness impregnation using H2PtCl6 x 6H2O as precursor substance. The removal efficiencies of oxalic acid by Pt/graphite, graphite catalyzed ozonation and ozonation alone were compared. It was found that the removal efficiency of oxalic acid in ozonation alone, graphite and Pt/graphite catalyzed ozonation was 3.0%, 47.6% and 99.3% respectively under the present experimental conditions. Results showed that loading of Pt could significantly increase the catalytic activity of graphite. Taking oxalic acid degradation efficiency as indication, the preparation conditions of Pt/graphite were optimized. The pretreatment of graphite had no favor to improve the activity of Pt/graphite catalyst. The optimal preparation conditions of Pt/graphite catalyst are as follow: impregnant, distilled water; impregnation time, 24 h; the loading amount of Pt, 1.0%; reduction temperature, 35 degrees C. The Pt/graphite catalyst was used for five times with no significant decrease of its activity and more than 90% oxalic acid removal was obtained. PMID:17674732

  14. Alleviation of chilling injury in tomato fruit by exogenous application of oxalic acid.

    PubMed

    Li, Peiyan; Yin, Fei; Song, Lijun; Zheng, Xiaolin

    2016-07-01

    The effects of oxalic acid on the development of chilling injury (CI), energy metabolism and lycopene metabolism in tomato fruit (Solanum lycopersicum L.) were investigated. Mature green tomatoes were dipped in 10mmoll(-1) oxalic acid (OA) solution for 10min at 25°C. Tomatoes were subsequently stored at 4±0.5°C for 20days before being transferred to 25°C for 12days. Oxalic acid treatment apparently alleviated CI development and membrane damage; maintained higher levels of ATP and ADP; increased activities of succinic dehydrogenase (SDH), Ca(2+)-adenosine triphosphatase (Ca(2+)-ATPase) and H(+)-adenosine triphosphatase (H(+)-ATPase); and elevated lycopene accumulation associated with the upregulation of PSY1 and ZDS expression in tomatoes during a period at room temperature following exposure to chilling stress. Thus, oxalic acid treatment benefited the control of CI and the maintenance of fruit quality in tomatoes stored for long periods (approximately 32days). PMID:26920276

  15. YfdW and YfdU are required for oxalate-induced acid tolerance in Escherichia coli K-12.

    PubMed

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

    2013-04-01

    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.

  16. 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

  17. Spectra investigation on surface characteristics of graphene oxide nanosheets treated with tartaric, malic and oxalic acids.

    PubMed

    Teng, Xiyao; Yan, Manqing; Bi, Hong

    2014-01-24

    The surface characteristics of graphene oxide nanosheets (GO) treated respectively with tartaric acid, malic acid and oxalic acid, have been investigated by mainly using optical spectroscopic methods including Fourier transform infrared spectroscopy (FT-IR), Ultraviolet-visible (UV-Vis) absorption and Raman spectroscopy. Additionally, the electrochemical property of the products has also been studied. The data revealed that oxygen-containing groups such as OH, COOH and CO on the GO surface have been almost removed and thus reduced graphene oxide nanosheets (RGN) were obtained. Interestingly, the number of sp(2) domains of RGN increases as treated by tartaric acidacid acid whereas the steric hindrance (SH) decreases and the ionization constant (IC) differs among these three acids. Furthermore, the specific capacitances (Cs) of GO have been greatly promoted from 2.4 F g(-1) to 100.8, 112.4, and 147 F g(-1) after treated with tartaric, malic and oxalic acids, respectively. This finding agrees well with the spectra result of the tendency of surface conjugated degree alteration. We claim that the difference in both SH and IC among these acids is the main reason for the diverse surface characteristics as well as the improved Cs of the RGN.

  18. Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid.

    PubMed

    Su, Xiaojuan; Zhu, Jun; Fu, Qingling; Zuo, Jichao; Liu, Yonghong; Hu, Hongqing

    2015-02-01

    Understanding the effects of oxalic acid (OA) on the immobilization of Pb(II) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(II) by KH2PO4, phosphate rock (PR), activated phosphate rock (APR) and synthetic hydroxyapatite (HAP) at different phosphate:Pb (P:Pb) molar ratios (0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or CaCl2, Community Bureau of Reference (BCR) sequential extraction and toxicity characteristic leaching procedure (TCLP) methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after 120 days was reduced by 100% when soils were amended with APR, HAP and HAP+OA, and the TCLP-Pb was <5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was <5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.

  19. In Situ Oxalic Acid Injection to Accelerate Arsenic Remediation at a Superfund Site in New Jersey

    PubMed Central

    Wovkulich, Karen; Stute, Martin; Mailloux, Brian J.; Keimowitz, Alison R.; Ross, James; Bostick, Benjamin; Sun, Jing; Chillrud, Steven N.

    2015-01-01

    Arsenic is a prevalent contaminant at a large number of US Superfund sites; establishing techniques that accelerate As remediation could benefit many sites. Hundreds of tons of As were released into the environment by the Vineland Chemical Co. in southern New Jersey during its manufacturing lifetime (1949–1994), resulting in extensive contamination of surface and subsurface soils and sediments, groundwater, and the downstream watershed. Despite substantial intervention at this Superfund site, sufficient aquifer cleanup could require many decades if based on traditional pump and treat technologies only. Laboratory column experiments have suggested that oxalic acid addition to contaminated aquifer solids could promote significant As release from the solid phase. To evaluate the potential of chemical additions to increase As release in situ and boost treatment efficiency, a forced gradient pilot scale study was conducted on the Vineland site. During spring/summer 2009, oxalic acid and bromide tracer were injected into a small portion (~50 m2) of the site for 3 months. Groundwater samples indicate that introduction of oxalic acid led to increased As release. Between 2.9 and 3.6 kg of As were removed from the sampled wells as a result of the oxalic acid treatment during the 3-month injection. A comparison of As concentrations on sediment cores collected before and after treatment and analyzed using X-ray fluorescence spectroscopy suggested reduction in As concentrations of ~36% (median difference) to 48% (mean difference). While further study is necessary, the addition of oxalic acid shows potential for accelerating treatment of a highly contaminated site and decreasing the As remediation time-scale. PMID:25598701

  20. Correlation between the production of exopolysaccharides and oxalic acid secretion by Ganoderma applanatum and Tyromyces palustris.

    PubMed

    Osińska-Jaroszuk, Monika; Wlizło, Kamila; Szałapata, Katarzyna; Jarosz-Wilkołazka, Anna

    2014-12-01

    The secretion of exopolysaccharides and oxalic acid in cultures of a white rot Ganoderma applanatum strain and a brown rot Tyromyces palustris strain were tested in terms of culture time, pH range, and temperature. The high yield of exopolysaccharides (EPS) required a moderate temperature of 28 °C for G. applanatum and 20 °C for T. palustris. G. applanatum and T. palustris accumulated more EPS when the concentration of the carbon source (maltose for G. applanatum and fructose for T. palustris) was 30 g/L. The results indicate that the production of oxalic acid by G. applanatum is correlated with the initial pH value of the culture medium and the concentration of oxalic acid increased to 1.66 ± 0.2 mM at the initial pH of 6.5 during the fungal growth. During the growth of T. palustris, the reduction of the initial pH value of the growing medium lowered the oxalic acid concentration from 7.7 ± 0.6 mM at pH 6.0 to 1.99 ± 0.2 mM at pH 3.5. T. palustris accumulated considerably more oxalic acid than G. applanatum and its presence did not affect significantly the production of exopolysaccharides. We also observed that the maximum amounts of exopolysaccharides secreted during cultivation of G. applanatum and T. palustris were 45.8 ± 1.2 and 19.1 ± 1.2 g/L, respectively.

  1. Evaluation Of Sludge Heel Dissolution Efficiency With Oxalic Acid Cleaning At Savannah River Site

    SciTech Connect

    Sudduth, Christie; Vitali, Jason; Keefer, Mark

    2014-01-08

    The chemical cleaning process baseline strategy at the Savannah River Site was revised to improve efficiency during future execution of the process based on lessons learned during previous bulk oxalic acid cleaning activities and to account for operational constraints imposed by safety basis requirements. These improvements were also intended to transcend the difficulties that arise from waste removal in higher rheological yield stress sludge tanks. Tank 12 implemented this improved strategy and the bulk oxalic acid cleaning efforts concluded in July 2013. The Tank 12 radiological removal results were similar to previous bulk oxalic acid cleaning campaigns despite the fact that Tank 12 contained higher rheological yield stress sludge that would make removal more difficult than the sludge treated in previous cleaning campaigns. No appreciable oxalate precipitation occurred during the cleaning process in Tank 12 compared to previous campaigns, which aided in the net volume reduction of 75-80%. Overall, the controls established for Tank 12 provide a template for an improved cleaning process.

  2. Dilute oxalic acid pretreatment for high total sugar recovery in pretreatment and subsequent enzymatic hydrolysis.

    PubMed

    Qing, Qing; Huang, Meizi; He, Yucai; Wang, Liqun; Zhang, Yue

    2015-12-01

    Oxalic acid was evaluated as an alternative reagent to mineral inorganic acid in pretreatment of corncob to achieve high xylose yield in addition to highly digestible solid residue. A quadratic polynomial model of xylose formation was developed for optimization of pretreatment process by the response surface methodology based on the impact factors of pretreatment temperature, reaction time, acid concentration, and solid-to-liquid ratio. The highest xylose yield was 94.3 % that was obtained under the pretreatment condition of 140 °C for 40 min with 0.5 wt% oxalic acid at a solid loading of 7.5 %. Under these conditions, the xylose yield results of verification experiments were very close to the model prediction, which indicated that the model was applicable. The solid residue generated under this condition also demonstrated a satisfactory enzymatic digestibility and fermentability. PMID:26494137

  3. An ATP and Oxalate Generating Variant Tricarboxylic Acid Cycle Counters Aluminum Toxicity in Pseudomonas fluorescens

    PubMed Central

    Singh, Ranji; Lemire, Joseph; Mailloux, Ryan J.; Chénier, Daniel; Hamel, Robert; Appanna, Vasu D.

    2009-01-01

    Although the tricarboxylic acid (TCA) cycle is essential in almost all aerobic organisms, its precise modulation and integration in global cellular metabolism is not fully understood. Here, we report on an alternative TCA cycle uniquely aimed at generating ATP and oxalate, two metabolites critical for the survival of Pseudomonas fluorescens. The upregulation of isocitrate lyase (ICL) and acylating glyoxylate dehydrogenase (AGODH) led to the enhanced synthesis of oxalate, a dicarboxylic acid involved in the immobilization of aluminum (Al). The increased activity of succinyl-CoA synthetase (SCS) and oxalate CoA-transferase (OCT) in the Al-stressed cells afforded an effective route to ATP synthesis from oxalyl-CoA via substrate level phosphorylation. This modified TCA cycle with diminished efficacy in NADH production and decreased CO2-evolving capacity, orchestrates the synthesis of oxalate, NADPH, and ATP, ingredients pivotal to the survival of P. fluorescens in an Al environment. The channeling of succinyl-CoA towards ATP formation may be an important function of the TCA cycle during anaerobiosis, Fe starvation and O2-limited conditions. PMID:19809498

  4. Seasonal characteristics of oxalic acid and related SOA in the free troposphere of Mt. Hua, central China: implications for sources and formation mechanisms.

    PubMed

    Meng, Jingjing; Wang, Gehui; Li, Jianjun; Cheng, Chunlei; Ren, Yanqin; Huang, Yao; Cheng, Yuting; Cao, Junji; Zhang, Ting

    2014-09-15

    PM10 aerosols from the summit of Mt. Hua (2060 m a.s.l) in central China during the winter and summer of 2009 were analyzed for dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls. Molecular composition of dicarboxylic acids (C2-C11) in the free tropospheric aerosols reveals that oxalic acid (C2, 399 ± 261 ng m(-3) in winter and 522 ± 261 ng m(-3) in summer) is the most abundant species in both seasons, followed by malonic (C3) and succinic (C4) acids, being consistent with that on ground levels. Most of the diacids are more abundant in summer than in winter, but adipic (C6) and phthalic (Ph) acids are twice lower in summer, suggesting more significant impact of anthropogenic pollution on the wintertime alpine atmosphere. Moreover, glyoxal (Gly) and methylglyoxal (mGly) are also lower in summer (12 ± 6.1 ng m(-3)) than in winter (22 ± 13 ng m(-3)). As both dicarbonyls are a major precursor of C2, their seasonal variation patterns, which are opposite to those of the diacids, indicate that the mountain troposphere is more oxidative in summer. C2 showed strong linear correlations with levoglucosan in winter and oxidation products of isoprene and monoterpene in summer. PCA analysis further suggested that the wintertime C2 and related SOA in the Mt. Hua troposphere mostly originate from photochemical oxidations of anthropogenic pollutants emitted from biofuel and coal combustion in lowland regions. On contrast, the summertime C2 and related SOA mostly originate from further oxidation of the mountainous isoprene and monoterpene oxidation products. The AIM model calculation results showed that oxalic acid concentration well correlated with particle acidity (R(2)=0.60) but not correlated with particle liquid water content, indicating that particle acidity favors the organic acid formation because aqueous-phase C2 production is the primary mechanism of C2 formation in ambient aerosols and is driven by acid-catalyzed oxidation. PMID:24925591

  5. IN-SITU MONITORING OF CORROSION DURING A LABORATORY SIMULATION OF OXALIC ACID CHEMICAL CLEANING

    SciTech Connect

    Wiersma, B; John Mickalonis, J; Michael Poirier, M; John Pareizs, J; David Herman, D; David Beam, D; Samuel Fink, S; Fernando Fondeur, F

    2007-10-08

    The Savannah River Site (SRS) will disperse or dissolve precipitated metal oxides as part of radioactive waste tank closure operations. Previously SRS used oxalic acid to accomplish this task. To better understand the conditions of oxalic acid cleaning of the carbon steel waste tanks, laboratory simulations of the process were conducted to determine the corrosion rate of carbon steel and the generation of gases such as hydrogen and carbon dioxide. Open circuit potential measurements, linear polarization measurements, and coupon immersion tests were performed in-situ to determine the corrosion behavior of carbon steel during the demonstration. Vapor samples were analyzed continuously to determine the constituents of the phase. The combined results from these measurements indicated that in aerated environments, such as the tank, that the corrosion rates are manageable for short contact times and will facilitate prediction and control of the hydrogen generation rate during operations.

  6. ELECTROCHEMICAL STUDIES ON THE CORROSION OF CARBON STEEL IN OXALIC ACID CLEANING SOLUTIONS

    SciTech Connect

    Wiersma, B; John Mickalonis, J

    2007-10-08

    The Savannah River Site (SRS) will disperse or dissolve precipitated metal oxides as part of radioactive waste tank closure operations. Previously SRS has utilized oxalic acid to accomplish this task. Since the waste tanks are constructed of carbon steel, a significant amount of corrosion may occur. Although the total amount of corrosion may be insignificant for a short contact time, a significant amount of hydrogen may be generated due to the corrosion reaction. Linear polarization resistance and anodic/cathodic polarization tests were performed to investigate the corrosion behavior during the process. The effect of process variables such as temperature, agitation, aeration, sample orientation, light as well as surface finish on the corrosion behavior were evaluated. The results of the tests provided insight into the corrosion mechanism for the iron-oxalic acid system.

  7. Oxidation of ferrocene by thiocyanic acid in the presence of ammonium oxalate

    NASA Astrophysics Data System (ADS)

    Ruslin, Farah bt; Yamin, Bohari M.

    2014-09-01

    A flake-like crystalline salt was obtained from the reaction of ferrocene, oxalic acid and ammonium thiocyanate in ethanol The elemental analysis and spectroscopic data were in agreement with the preliminary X-ray molecular structure. The compound consists of four ferrocenium moieties and a counter anion consisting of two (tetraisothiocyanato)iron(III) linked by an oxalato bridging group in such a way that both iron central atoms adopt octahedral geometries.

  8. Oxidation of ferrocene by thiocyanic acid in the presence of ammonium oxalate

    SciTech Connect

    Ruslin, Farah bt; Yamin, Bohari M.

    2014-09-03

    A flake-like crystalline salt was obtained from the reaction of ferrocene, oxalic acid and ammonium thiocyanate in ethanol The elemental analysis and spectroscopic data were in agreement with the preliminary X-ray molecular structure. The compound consists of four ferrocenium moieties and a counter anion consisting of two (tetraisothiocyanato)iron(III) linked by an oxalato bridging group in such a way that both iron central atoms adopt octahedral geometries.

  9. Removal of oxalic acid, oxamic acid and aniline by a combined photolysis and ozonation process.

    PubMed

    Orge, C A; Faria, J L; Pereira, M F R

    2015-01-01

    Aniline (ANL), an aromatic amine, oxalic acid (OXA) and oxamic acid (OMA), short-chain carboxylic acids, were chosen as model organic pollutants for testing the combined effect of neat photolysis and ozonation in the treatment of aqueous effluents. In order to better understand the results, single ozonation and neat photolysis were also carried out. OXA has a high refractory character relatively to single ozonation and neat photolysis only accounted for 26% conversion of OXA after 2 h of reaction. On the other hand, OXA complete degradation was observed in less than an hour when ozone and light were used simultaneously. Despite OMA, a compound never studied before by a combined ozonation and photolysis treatment, being highly refractory to oxidation, more than 50% was removed by photo-ozonation after 3 h of reaction. In the case of ANL, both single ozonation and photo-ozonation resulted in 100% removal in a short reaction period due to the high reactivity of ozone to attack this type of molecules; however, only the combined method leads to efficient mineralization (89%) after 3 h of reaction. A significant synergetic effect was observed in the degradation of the selected contaminants by the simultaneous use of ozone and light, since the mineralization rate of combined method is higher than the sum of the mineralization rates of the individual treatments. The promising results observed in the degradation of the selected contaminants are paving the way to the application of photo-ozonation in the treatment of wastewater containing this type of pollutants.

  10. Field assessment of yeast- and oxalic Acid-generated carbon dioxide for mosquito surveillance.

    PubMed

    Harwood, James F; Richardson, Alec G; Wright, Jennifer A; Obenauer, Peter J

    2014-12-01

    Carbon dioxide (CO2) sources improve the efficacy of mosquito traps. However, traditional CO2 sources (dry ice or compressed gas) may be difficult to acquire for vector surveillance during military contingency operations. For this reason, a new and convenient source of CO2 is required. Two novel CO2 generators were evaluated in order to address this capability gap: 1) an electrolyzer that converts solid oxalic acid into CO2 gas, and 2) CO2 produced by yeast as it metabolizes sugar. The flow rate and CO2 concentration produced by each generator were measured, and each generator's ability to attract mosquitoes to BG-Sentinel™ traps during day surveillance and to Centers for Disease Control and Prevention light traps with incandescent bulbs during night surveillance was compared to dry ice and compressed gas in Jacksonville, FL. The electrolyzed oxalic acid only slightly increased the number of mosquitoes captured compared to unbaited traps. Based on the modest increase in mosquito collection for traps paired with the oxalic acid, it is not a suitable stand-in for either of the 2 traditional CO2 sources. Conversely, the yeast-generated CO2 resulted in collections with mosquito abundance and species richness more closely resembling those of the traditional CO2 sources, despite achieving a lower CO2 flow rate. Therefore, if dry ice or compressed gas cannot be acquired for vector surveillance, yeast-generated CO2 can significantly improve trap capability. PMID:25843133

  11. Evidence of Polaron Excitations in Low Temperature Raman Spectra of Oxalic Acid Dihydrate.

    PubMed

    Mohaček-Grošev, Vlasta; Grdadolnik, Jože; Hadži, Dušan

    2016-05-12

    Low temperature Raman spectra of oxalic acid dihydrate (8-300 K) for both the polycrystalline and single crystal phase show strong variation with temperature in the interval from 1200 to 2000 cm(-1). Previous low temperature diffraction studies all confirmed the stability of the crystal P21/n phase with no indications of any phase transition, reporting the existence of a strong hydrogen bond between the oxalic acid and a water molecule. A new group of Raman bands in the 1200-1300 cm(-1) interval below 90 K is observed, caused by possible loss of the center of inversion. This in turn could originate either due to disorder in hydroxyl proton positions or due to proton transfer from carboxylic group to water molecule. The hypothesis of proton transfer is further supported by the emergence of new bands centered at 1600 and 1813 cm(-1), which can be explained with vibrations of H3O(+) ions. The broad band at 1600 cm(-1) looses intensity, while the band at 1813 cm(-1) gains intensity on cooling. The agreement between quantum calculations of vibrational spectra and experimentally observed Raman bands of hydronium ions in oxalic acid sesquihydrate crystal corroborates this hypothesis. PMID:27093217

  12. Oxalate catabolism in Arabidopsis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Oxalic acid is found in most plant species and can serve beneficial roles that protect the plant from a variety of environmental stresses. Excessive amounts of oxalate, however, can be detrimental to plant health. Thus, careful coordination of oxalate metabolism is needed. Despite the important impa...

  13. [EXPERIENCE OF USE OF BLEMAREN® IN THE TREATMENT OF PATIENTS IN URIC ACID AND CALCIUM OXALATE UROLITHIASIS].

    PubMed

    Konstantinova, O V; Yanenko, E K

    2015-01-01

    154 patients with urolithiasis were under outpatient observation for 2-8 years. Among them there were 76 women and 78 men aged 21-66 years, of which 46 patients with uric acid urolithiasis, and 88--with calcium oxalate urolithiasis. Treatment of patients was carried out systematically, depending on their condition. Indications for the application of Blemaren® included the presence of uric acid stones, uric acid and/or oxalate crystalluria. The duration of treatment was 6.1 months. The dosage of the drug varied from 6 to 18 g per day and was selected individually, depending on the purpose of the appointment of Blemaren®. Reduction of the urine pH to 6.2- 6.8-7.2 was the criterion for properly selected dose. To dissolve uric acid stones in the presence of hyperuricemia and/or hyperuricuria, Blemaren® was administered in combination with allopurinol at a dose of 0.1 g 3-4 times a day. Besides pharmacotherapy, treatment included diet therapy. It was found that the morning urine pH in urate urolithiasis is sustainable and has a range of 5.0-6.0, in 80.4% of cases--range of 5.0-5.5. In calcium oxalate urolithiasis this parameter is also stable and has a range of 5.0-6.7, in 82.9% of cases--range of 5.5-6.0. Optimal urine pH to eliminate uric acid and oxalate crystalluria in patients with uric acid and calcium oxalate urolithiasis is the interval of 6.2-6.4. It was shown that Blemaren® is a highly effective agent for treatment and prevention of uric acid and calcium oxalate crystalluria in calcium oxalate and uric acid urolithiasis. Further, its effectiveness in dissolving of uric acid stones in the absence of an infectious inflammatory process is 82.3%. PMID:26859932

  14. Evaluation of an acid ammonium oxalate extraction to determine fluoride resident concentrations in soils.

    PubMed

    Bégin, Louis; Fortin, Josée

    2003-01-01

    Fluoride depositions near aluminum smelters and other fluoride-emitting plants can lead to fluoride accumulation in soils, which constitutes a risk for ground water contamination. This study was conducted to investigate the capacity of a 0.2 M acid ammonium oxalate solution to selectively and quantitatively extract fluoride accumulated in soils. The recovery of fluoride added to three soils was evaluated following 7- to 28-d incubations. Oxalate extraction was also compared with a total fluoride extraction method, using oxalate-extractable fluoride (Fox) and total fluoride (Ftot) accumulation profiles derived from column percolation experiments. To determine low-level fluoride concentrations without interference from high Al and Fe concentrations, an adapted ion chromatography method was used. Following soil incubations, oxalate extracted 42 to 86% of added fluoride. Recovery varied between soils and, in one soil, increased with added fluoride concentration. Recovery was unaffected by incubation time. Maximum recovery was obtained in a soil high in amorphous Fe and Al, low in clay, and free of carbonate. Lower recoveries were obtained in soils with higher clay or carbonate contents. Only 4 to 8% of Ftot was extracted in untreated samples using Fox, which suggests a high selectivity of this method for added fluoride. In percolation experiments, the use of Fox reduced considerably the background noise associated with Ftot for the evaluation of fluoride accumulation profiles. Because of its high selectivity and despite incomplete fluoride recovery, the use of Fox to determine fluoride resident concentrations in soils may improve environmental monitoring of fluoride accumulation and movement in contaminated soils.

  15. 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

  16. DEPOSITION TANK CORROSION TESTING FOR ENHANCED CHEMICAL CLEANING POST OXALIC ACID DESTRUCTION

    SciTech Connect

    Mickalonis, J.

    2011-08-29

    An Enhanced Chemical Cleaning (ECC) process is being developed to aid in the high level waste tank closure at the Savannah River Site. The ECC process uses an advanced oxidation process (AOP) to destroy the oxalic acid that is used to remove residual sludge from a waste tank prior to closure. The AOP process treats the dissolved sludge with ozone to decompose the oxalic acid through reactions with hydroxyl radicals. The effluent from this oxalic acid decomposition is to be sent to a Type III waste tank and may be corrosive to these tanks. As part of the hazardous simulant testing that was conducted at the ECC vendor location, corrosion testing was conducted to determine the general corrosion rate for the deposition tank and to assess the susceptibility to localized corrosion, especially pitting. Both of these factors impact the calculation of hydrogen gas generation and the structural integrity of the tanks, which are considered safety class functions. The testing consisted of immersion and electrochemical testing of A537 carbon steel, the material of construction of Type III tanks, and 304L stainless steel, the material of construction for transfer piping. Tests were conducted in solutions removed from the destruction loop of the prototype ECC set up. Hazardous simulants, which were manufactured at SRNL, were used as representative sludges for F-area and H-area waste tanks. Oxalic acid concentrations of 1 and 2.5% were used to dissolve the sludge as a feed to the ECC process. Test solutions included the uninhibited effluent, as well as the effluent treated for corrosion control. The corrosion control options included mixing with an inhibited supernate and the addition of hydroxide. Evaporation of the uninhibited effluent was also tested since it may have a positive impact on reducing corrosion. All corrosion testing was conducted at 50 C. The uninhibited effluent was found to increase the corrosion rate by an order of magnitude from less than 1 mil per year (mpy

  17. Adsorption and oxidation of oxalic acid on anatase TiO2 (001) surface: A density functional theory study.

    PubMed

    Sun, Tao; Wang, Yun; Zhang, Haimin; Liu, Porun; Zhao, Huijun

    2015-09-15

    Anatase TiO2 (001) surfaces have attracted great interest for photo-degradation of organic species recently due to their high reactivity. In this work, adsorption properties and oxidation mechanisms of oxalic acid on the anatase TiO2 (001) surface have been theoretically investigated using the first-principles density functional theory. Various possible adsorption configurations are considered by diversifying the connectivity of carboxylic groups with the surface. It is found that the adsorption of oxalic acid on the anatase (001) surface prefer the dissociative states. A novel double-bidentate configuration has been found due to the structural match between oxalic acid and the (001) surface. More charge is transferred from the adsorbed oxalic acid to the surface with the double-bidentate configuration when comparing with other adsorption structures. Thus, there is a positive correlation relationship between the transferred charge amount and the interfacial bond numbers when oxalic acid adsorbs on the anatase TiO2 (001) surface. The adsorption energies with dispersion corrections have demonstrated that the van der Waals interactions play an important role in the adsorption, especially when adsorbates are close to the surface.

  18. Polyacrylonitrile/manganese acetate composite nanofibers and their catalysis performance on chromium (VI) reduction by oxalic acid.

    PubMed

    Zhang, Chengcheng; Li, Xiang; Bian, Xiujie; Zheng, Tian; Wang, Ce

    2012-08-30

    Polyacrylonitrile(PAN)/manganese acetate(Mn(CH(3)COO)(2)) composite nanofibers have been fabricated by electrospinning, a simple and effective technology. The obtained composite nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectrometer (FT-IR). The composite nanofibers are amorphous in structure, continuous, even and smooth. At the same time, the reduction performance of Cr(VI) by oxalic acid in the presence of the composite nanofibers is also investigated. The results indicate that the composite nanofibers have exhibited excellent catalysis performance for Cr(VI) reduction from a Cr(2)O(7)(2-)-containing solution by oxalic acid. And the critical parameters, such as the catalyst dosage, oxalic acid content, chromium concentration, the pH value of the reaction solution and light have important impact on the reduction process. Under the simulated solar light irradiation, after only 60 min, 1.2mM initial Cr(VI) solution was reduced absolutely in the presence of PAN/Mn(CH(3)COO)(2) composite nanofibers containing 17.5 wt.% Mn(CH(3)COO)(2) by 0.3 mL 0.5M oxalic acid. In light, the reduction of Cr(VI) by oxalic acid is markedly accelerated. PMID:22709851

  19. CORROSION TESTING OF CARBON STEEL IN OXALIC ACID CHEMICAL CLEANING SOLUTIONS

    SciTech Connect

    Wiersma, B.; Mickalonis, J.; Subramanian, K.; Ketusky, E.

    2011-10-14

    Radioactive liquid waste has been stored in underground carbon steel tanks for nearly 60 years at the Savannah River Site. The site is currently in the process of removing the waste from these tanks in order to place it into vitrified, stable state for longer term storage. The last stage in the removal sequence is a chemical cleaning step that breaks up and dissolves metal oxide solids that cannot be easily pumped out of the tank. Oxalic acid has been selected for this purpose because it is an effective chelating agent for the solids and is not as corrosive as other acids. Electrochemical and immersion studies were conducted to investigate the corrosion behavior of carbon steel in simulated chemical cleaning environments. The effects of temperature, agitation, and the presence of sludge solids in the oxalic acid on the corrosion rate and the likelihood of hydrogen evolution were determined. The testing showed that the corrosion rates decreased significantly in the presence of the sludge solids. Corrosion rates increased with agitation, however, the changes were less noticeable.

  20. Ted Malone: Broadcast Interpretationist.

    ERIC Educational Resources Information Center

    Gibson, J. S.

    One of the few broadcast interpretationists recorded in the history of radio, Frank Alden Russell--whose Ted Malone programs spanned three decades on local stations and national networks--perhaps best represents both the initiation and prime of broadcast interpretation. Born in 1908, Russell became interested in oral performance when he was…

  1. Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid.

    PubMed

    Zeng, Xianlai; Li, Jinhui; Shen, Bingyu

    2015-09-15

    With the booming of consumer electronics (CE) and electric vehicle (EV), a large number of spent lithium-ion battery (LIBs) have been generated worldwide. Resource depletion and environmental concern driven from the sustainable industry of CE and EV have motivated spent LIBs should be recovered urgently. However, the conventional process combined with leaching, precipitating, and filtering was quite complicated to recover cobalt and lithium from spent LIBs. In this work, we developed a novel recovery process, only combined with oxalic acid leaching and filtering. When the optimal parameters for leaching process is controlled at 150 min retention time, 95 °C heating temperature, 15 g L(-1) solid-liquid ratio, and 400 rpm rotation rate, the recovery rate of lithium and cobalt from spent LIBs can reach about 98% and 97%, respectively. Additionally, we also tentatively discovered the leaching mechanism of lithium cobalt oxide (LiCoO2) using oxalic acid, and the leaching order of the sampling LiCoO2 of spent LIBs. All the obtained results can contribute to a short-cut and high-efficiency process of spent LIBs recycling toward a sound closed-loop cycle.

  2. Melaminium hydrogen malonate

    PubMed Central

    Froschauer, Barbara; Weil, Matthias

    2012-01-01

    The melaminium (2,4,6-triamino-1,3,5-triazin-1-ium) cation in the title compound, C3H7N6 +·C3H3O4 −, is essentially planar, with a r.m.s. deviation of the non-H atoms of 0.0085 Å. Extensive hydrogen bonding of the types N—H⋯N and N—H⋯O between cations and cations and between cations and hydrogen malonate (2-carb­oxy­ethano­ate) anions leads to the formation of supra­molecular layers parallel to (1-2-1). An intra­molecular O—H⋯O hydrogen bond in the single deprotonated malonate anion also occurs. PMID:22904984

  3. Poly(acrylic acid) to induce competitive crystallization of a theophylline/oxalic acid cocrystal and a theophylline polymorph

    NASA Astrophysics Data System (ADS)

    Jang, Jisun; Kim, Il Won

    2016-01-01

    Polymeric additives to induce competitive crystallization of pharmaceutical compounds were explored. A cocrystal of theophylline and oxalic acid was used as a model system, and poly(acrylic acid), poly(caprolactone), and poly(ethylene glycol) were the additives. The cocrystal formation was selectively hindered with addition of poly(acrylic acid). First the size of the cocrystals were reduced, and eventually the cocrystallization was inhibited to generate neat theophylline crystals. The theophylline crystals were of a distinctively different crystal structure from known polymorphs, based on powder X-ray diffraction. They were also obtained in nanoscale size, when millimeter-scale crystals formed without poly(acrylic acid). Polymeric additives that could form specific interactions with crystallizing compounds seem to be useful tools for the phase and size control of pharmaceutical crystals.

  4. A Neat Trick Using Oxalic Acid Dihydrate and Potassium Permanganate and Other Experiments with Small Organic Amine or Oxygenated Compounds

    ERIC Educational Resources Information Center

    Kelland, Malcolm A.

    2011-01-01

    Solid potassium permanganate (KMnO[subscript 4]) is shown to react in a variety of ways with small organic amines or oxygenated compounds depending on whether they are liquids or solids and whether water is present. In particular, its reaction with solid oxalic acid dihydrate can be initiated by the moisture in one's breath, making an intriguing…

  5. Proteomic and Biochemical Studies of Lysine Malonylation Suggest Its Malonic Aciduria-associated Regulatory Role in Mitochondrial Function and Fatty Acid Oxidation.

    PubMed

    Colak, Gozde; Pougovkina, Olga; Dai, Lunzhi; Tan, Minjia; Te Brinke, Heleen; Huang, He; Cheng, Zhongyi; Park, Jeongsoon; Wan, Xuelian; Liu, Xiaojing; Yue, Wyatt W; Wanders, Ronald J A; Locasale, Jason W; Lombard, David B; de Boer, Vincent C J; Zhao, Yingming

    2015-11-01

    The protein substrates of sirtuin 5-regulated lysine malonylation (Kmal) remain unknown, hindering its functional analysis. In this study, we carried out proteomic screening, which identified 4042 Kmal sites on 1426 proteins in mouse liver and 4943 Kmal sites on 1822 proteins in human fibroblasts. Increased malonyl-CoA levels in malonyl-CoA decarboxylase (MCD)-deficient cells induces Kmal levels in substrate proteins. We identified 461 Kmal sites showing more than a 2-fold increase in response to MCD deficiency as well as 1452 Kmal sites detected only in MCD-/- fibroblast but not MCD+/+ cells, suggesting a pathogenic role of Kmal in MCD deficiency. Cells with increased lysine malonylation displayed impaired mitochondrial function and fatty acid oxidation, suggesting that lysine malonylation plays a role in pathophysiology of malonic aciduria. Our study establishes an association between Kmal and a genetic disease and offers a rich resource for elucidating the contribution of the Kmal pathway and malonyl-CoA to cellular physiology and human diseases. PMID:26320211

  6. Use of 2-(6-mercaptohexyl) malonic acid to adjust the morphology and electret properties of cyclic olefin copolymer and its application to flexible loudspeakers

    NASA Astrophysics Data System (ADS)

    Ko, Wen-Ching; Tseng, Chien-Kai; Leu, Ing-Yih; Wu, Wen-Jong; Shih-Yuan Lee, Adam; Lee, Chih-Kung

    2010-05-01

    Recent uses of flexible electret loudspeakers in futuristic applications have garnered much interest for these novel loudspeakers. In this paper, a novel thin film processing method was developed to improve the performance of an electret diaphragm. This paper discusses the relationship between the charge storage and the additive concentration. A cyclic olefin copolymer (COC) thin film containing an additive such as 2-(6-mercaptohexyl) malonic acid was prepared using a spin-coating process. Furthermore, attention was directed towards the processing conditions which were found to have an important role and are related to the self-assembly and micelle formation behavior of the additives in the COC. In the present study, thin films of 13 µm thickness were charged by a corona method. Compared with a reference thin film of pure COC, results indicated that when a 3497 mg kg - 1 additive was added to the COC matrix, the obtained surface potential was 71% higher. Thus, the results show that a COC + additive thin film leads to a much improved charge storage. It appears to be an inexpensive and relatively easy way to form a thin structure for developing novel flexible electret loudspeakers.

  7. Screening of indigenous oxalate degrading lactic acid bacteria from human faeces and South Indian fermented foods: assessment of probiotic potential.

    PubMed

    Gomathi, Sivasamy; Sasikumar, Ponnusamy; Anbazhagan, Kolandaswamy; Sasikumar, Sundaresan; Kavitha, Murugan; Selvi, M S; Selvam, Govindan Sadasivam

    2014-01-01

    Lactic acid bacteria (LAB) have the potential to degrade intestinal oxalate and this is increasingly being studied as a promising probiotic solution to manage kidney stone disease. In this study, oxalate degrading LAB were isolated from human faeces and south Indian fermented foods, subsequently assessed for potential probiotic property in vitro and in vivo. Based on preliminary characteristics, 251 out of 673 bacterial isolates were identified as LAB. A total of 17 strains were found to degrade oxalate significantly between 40.38% and 62.90% and were subjected to acid and bile tolerance test. Among them, nine strains exhibited considerable tolerance up to pH 3.0 and at 0.3% bile. These were identified as Lactobacillus fermentum and Lactobacillus salivarius using 16S rDNA sequencing. Three strains, Lactobacillus fermentum TY5, Lactobacillus fermentum AB1, and Lactobacillus salivarius AB11, exhibited good adhesion to HT-29 cells and strong antimicrobial activity. They also conferred resistance to kanamycin, rifampicin, and ampicillin, but were sensitive to chloramphenicol and erythromycin. The faecal recovery rate of these strains was observed as 15.16% (TY5), 6.71% (AB1), and 9.3% (AB11) which indicates the colonization ability. In conclusion, three efficient oxalate degrading LAB were identified and their safety assessments suggest that they may serve as good probiotic candidates for preventing hyperoxaluria.

  8. Screening of Indigenous Oxalate Degrading Lactic Acid Bacteria from Human Faeces and South Indian Fermented Foods: Assessment of Probiotic Potential

    PubMed Central

    Kavitha, Murugan; Selvi, M. S.; Selvam, Govindan Sadasivam

    2014-01-01

    Lactic acid bacteria (LAB) have the potential to degrade intestinal oxalate and this is increasingly being studied as a promising probiotic solution to manage kidney stone disease. In this study, oxalate degrading LAB were isolated from human faeces and south Indian fermented foods, subsequently assessed for potential probiotic property in vitro and in vivo. Based on preliminary characteristics, 251 out of 673 bacterial isolates were identified as LAB. A total of 17 strains were found to degrade oxalate significantly between 40.38% and 62.90% and were subjected to acid and bile tolerance test. Among them, nine strains exhibited considerable tolerance up to pH 3.0 and at 0.3% bile. These were identified as Lactobacillus fermentum and Lactobacillus salivarius using 16S rDNA sequencing. Three strains, Lactobacillus fermentum TY5, Lactobacillus fermentum AB1, and Lactobacillus salivarius AB11, exhibited good adhesion to HT-29 cells and strong antimicrobial activity. They also conferred resistance to kanamycin, rifampicin, and ampicillin, but were sensitive to chloramphenicol and erythromycin. The faecal recovery rate of these strains was observed as 15.16% (TY5), 6.71% (AB1), and 9.3% (AB11) which indicates the colonization ability. In conclusion, three efficient oxalate degrading LAB were identified and their safety assessments suggest that they may serve as good probiotic candidates for preventing hyperoxaluria. PMID:24723820

  9. Suppression of Growth Rate of Colony-Associated Fungi by High Fructose Corn Syrup Feeding Supplement, Formic Acid, and Oxalic Acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Select colony-associated fungi (bee isolates). Absidia sp., Ascosphaera apis, Aspergillus flavus, Fusarium sp., Penicillium glabrum, Mucor sp., showed a 40% reduction in radial growth rate with formic acid, a 28% reduction with oxalic acid, and a 15% reduction with fructose and high fructose corn sy...

  10. Corrosion Testing of Carbon Steel in Oxalic Acid that Contains Dissolved Iron

    SciTech Connect

    Wiersma, Bruce J.; Mickalonis, John I.; Subramanian, Karthik H.

    2012-10-11

    Radioactive liquid waste has been stored in underground carbon steel tanks for nearly 60 years at the Savannah River Site. The site is currently in the process of removing the waste from these tanks in order to place it into vitrified, stable state for longer term storage. The last stage in the removal sequence is a chemical cleaning step that breaks up and dissolves metal oxide solids that cannot be easily pumped out of the tank. Oxalic acid (OA) will be used to chemically clean the tanks after waste retrieval is completed. The waste tanks at SRS were constructed from carbon steel materials and thus are vulnerable to corrosion in acidic media. In addition to structural impacts, the impact of corrosion on the hydrogen generated during the process must be assessed. Electrochemical and coupon immersion tests were used to investigate the corrosion mechanism at anticipated process conditions. The testing showed that the corrosion rates were dependent upon the reduction of the iron species that had dissolved in solution. Initial corrosion rates were elevated due to the reduction of the ferric species to ferrous species. At later times, as the ferric species depleted, the corrosion rate decreased. On the other hand, the hydrogen evolution reaction became more dominant.

  11. Porous aluminum room temperature anodizing process in a fluorinated-oxalic acid solution

    NASA Astrophysics Data System (ADS)

    Dhahri, S.; Fazio, E.; Barreca, F.; Neri, F.; Ezzaouia, H.

    2016-08-01

    Anodizing of aluminum is used for producing porous insulating films suitable for different applications in electronics and microelectronics. Porous-type aluminum films are most simply realized by galvanostatic anodizing in aqueous acidic solutions. The improvement in application of anodizing technique is associated with a substantial reduction of the anodizing voltage at appropriate current densities as well as to the possibility to carry out the synthesis process at room temperature in order to obtain a self-planarizing dielectric material incorporated in array of super-narrow metal lines. In this work, the anodizing of aluminum to obtain porous oxide was carried out, at room temperature, on three different substrates (glass, stainless steel and aluminum), using an oxalic acid-based electrolyte with the addition of a relatively low amount of 0.4 % of HF. Different surface morphologies, from nearly spherical to larger porous nanostructures with smooth edges, were observed by means of scanning electron microscopy. These evidences are explained by considering the formation, transport and adsorption of the fluorine species which react with the Al3+ ions. The behavior is also influenced by the nature of the original substrate.

  12. The effect of citric and oxalic acid doping on the superconducting properties of MgB2

    NASA Astrophysics Data System (ADS)

    Ojha, N.; Malik, V. K.; Singla, Rashmi; Bernhard, C.; Varma, G. D.

    2009-12-01

    In this paper we report the effect of carbon doping on the structural and superconducting properties of MgB2 using citric and oxalic acids as carbon sources. The bulk polycrystalline samples have been synthesized via a standard solid state reaction route with composition MgB2+x wt% of citric and oxalic acids (x = 0, 5 and 10). The x-ray diffraction results reveal the formation of dominantly MgB2 with only a small amount of impurity phase MgO and substitution of C at the B site of MgB2 for both dopants. Improvements in the upper critical field (HC2), irreversibility field (Hirr) and high field (>2.5 T) critical current density (JC) have been observed on C doping in the samples. The correlations between superconducting properties and structural characteristics of the samples are described and discussed in this paper.

  13. Effect of Macerase, Oxalic Acid, and EGTA on Deep Supercooling and Pit Membrane Structure of Xylem Parenchyma of Peach.

    PubMed

    Wisniewski, M; Davis, G; Arora, R

    1991-08-01

    The object of this study was to determine if calcium cross-linking of pectin in the pit membrane of xylem parenchyma restricts water movement which results in deep supercooling. Current year shoots of ;Loring' peach (Prunus persica) were infiltrated with oxalic acid or EGTA solutions for 24 or 48 hours and then either prepared for ultrastructural analysis or subjected to differential thermal analysis. The effect of 0.25 to 1.0% pectinase (weight/volume) on deep supercooling was also investigated. The use of 5 to 50 millimolar oxalic acid and pectinase resulted in a significant reduction (flattening) of the low temperature exotherm and a distinct swelling and partial degradation of the pit membrane. EGTA (10 millimolar) for 24 or 48 hours shifted the low temperature exotherm to warmer temperatures and effected the outermost layer of the pit membrane. A hypothesis is presented on pectin-mediated regulation of deep supercooling of xylem parenchyma.

  14. A growth mechanism of porous film formed on Al in 0.6 M oxalic acid electrolyte.

    PubMed

    Han, Seong Ho; Kim, Hyoung Chan

    2012-04-01

    Understanding of mechanism of porous film formation is of fundamental importance for anodizing in general because, the onset of pore initiation terminates the barrier film growth process over the macroscopic metal surface. Several mechanisms have been proposed to explain pore formation. They include direct injection of aluminum ions into electrolyte and a field-assisted dissolution mechanism. High-resolution scanning electron microscopy of anodized surfaces and direct TEM of ion beam thinned films and ultrarmicrotomed film sections have been employed to gain further insight into the mechanism of initial porous film growth in 0.6 M oxalic acid. From detailed examination of the behavior of the xenon-tagged layer in the film during pore initiation and development in oxalic acid, the film structure of the barrier layer is found to be unstable during pore initiation and the instability of the film structure is possibly related to the field-assisted structure modification process.

  15. Fermentation parameter optimization of microbial oxalic acid production from cashew apple juice.

    PubMed

    Betiku, Eriola; Emeko, Harrison A; Solomon, Bamidele O

    2016-02-01

    The potential of cashew apple juice (CAJ) as a carbon source for oxalic acid (OA) production via fermentation process was investigated in this study. The effects and interactions of CAJ concentration, time, pH, NaNO3 concentration and methanol concentration on OA production were determined in a central composite design (CCD) and the process was modelled and optimized using response surface methodology (RSM). The results showed that OA fermentation can be described significantly (p < 0.05) by a quadratic model giving regression coefficient (R (2)) of 0.9964. NaNO3 concentration was the most significant positive variable while methanol was not a significant variable. A maximum OA concentration of 122.68 g/l could be obtained using the optimum levels of CAJ of 150.0 g/l, pH of 5.4, time of 7.31 days, NaNO3 of 2 g/l and methanol of 1% volume. The production of OA was found to increase from 106.75 to 122.68 g/l using the statistically design optimization. This study revealed that CAJ could serve as an inexpensive and abundant feedstock for fermentative OA production, the resulting model could be used in the design of a typical pilot plant for a scale up production.

  16. Mechanism of lead immobilization by oxalic acid-activated phosphate rocks.

    PubMed

    Jiang, Guanjie; Liu, Yonghong; Huang, Li; Fu, Qingling; Deng, Youjun; Hu, Hongqing

    2012-01-01

    Lead (Pb) chemical fixation is an important environmental aspect for human health. Phosphate rocks (PRs) were utilized as an adsorbent to remove Pb from aqueous solution. Raw PRs and oxalic acid-activated PRs (APRs) were used to investigate the effect of chemical modification on the Pb-binding capacity in the pH range 2.0-5.0. The Pb adsorption rate of all treatments above pH 3.0 reached 90%. The Pb binding on PRs and APRs was pH-independent, except at pH 2.0 in activated treatments. The X-ray diffraction analysis confirmed that the raw PRs formed cerussite after reacting with the Pb solution, whereas the APRs formed pyromorphite. The Fourier Transform Infrared spectroscopy analysis indicated that carbonate (CO3(2-)) in raw PRs and phosphate (PO4(3)) groups in APRs played an important role in the Pb-binding process. After adsorption, anomalous block-shaped particles were observed by scanning electron microscopy with energy dispersive spectroscopy. The X-ray photoelectron spectroscopy data further indicated that both chemical and physical reactions occurred during the adsorption process according to the binding energy. Because of lower solubility of pyromorphite compared to cerussite, the APRs are more effective in immobilizing Pb than that of PRs.

  17. Comparing oxalic acid and sucrocide treatments for Varroa destructor (Acari: Varroidae) control under desert conditions.

    PubMed

    Sammataro, D; Finley, J; Underwood, R

    2008-08-01

    The effectiveness of oxalic acid (OA) and Sucrocide (S) (AVA Chemical Ventures, L.L.C., Portsmouth, NH) in reducing populations of the varroa mite Varroa destructor Anderson & Trueman (Acari: Varroidae) in honey bee, Apis mellifera L. (Hymenoptera: Apidae) colonies was measured under the desert conditions of Arizona, USA. OA and S were applied three times 7 d apart. A 3.2% solution of OA was applied in sugar syrup via a large volume syringe, trickling 5 ml per space between frames in the colony. S was applied at a concentration of 0.625% (mixed with water), according to the label directions, using a compressed air Chapin sprayer at 20 psi to apply 59 ml per frame space. Varroa mites, collected on a sticky board before, during, and after the treatments, were counted to assess the effectiveness of the treatments. This study showed that a desert climate zone did not confer any positive or negative results on the acaricidal properties of OA. Even with brood present in colonies, significant varroa mite mortality occurred in the OA colonies. In contrast, we found that Sucrocide was not effective as a mite control technique. Despite its ability to increase mite mortality in the short-term, varroa mite populations measured posttreatment were not affected any more by Sucrocide than by no treatment at all.

  18. Esophageal mucosa exfoliation induced by oxalic acid poisoning: A case report

    PubMed Central

    WANG, JIERU; KAN, BAOTIAN; JIAN, XIANGDONG; WU, XIAOPENG; YU, GUANCAI; SUN, JING

    2016-01-01

    This study reports the case of a 44-year-old woman with oral oxalic acid poisoning. As the illness progressed, the patient exhibited severe metabolic acidosis, large-area esophageal mucosa injury and acute kidney injury, which required dialysis. A guide wire slipped out of position during the process of hemodialysis and moved back and forth in the veins, but was removed successfully by interventional endovascular treatment. However, the patient's esophageal mucosa exfoliated, which lead to severe benign esophageal stenosis and dysphagia. Balloon distention was conducted twice in the upper digestive tract using X-ray location in combination with a dumb-bell bladder and interventional wire. The patient exhibited convulsions, shock, embolism and loss of consciousness while undergoing the second balloon distention procedure. Following symptomatic treatment, the patient eventually remained in a stable condition, the digestive tract expansion procedure was not resumed and a jejunostomy was performed in order to facilitate enteral nutrition, which was administered via the jejunum and had little stimulatory effect on the pancreas. Following various treatments, the patient's condition improved markedly, with renal function returning to normal. PMID:26889241

  19. Fermentation parameter optimization of microbial oxalic acid production from cashew apple juice.

    PubMed

    Betiku, Eriola; Emeko, Harrison A; Solomon, Bamidele O

    2016-02-01

    The potential of cashew apple juice (CAJ) as a carbon source for oxalic acid (OA) production via fermentation process was investigated in this study. The effects and interactions of CAJ concentration, time, pH, NaNO3 concentration and methanol concentration on OA production were determined in a central composite design (CCD) and the process was modelled and optimized using response surface methodology (RSM). The results showed that OA fermentation can be described significantly (p < 0.05) by a quadratic model giving regression coefficient (R (2)) of 0.9964. NaNO3 concentration was the most significant positive variable while methanol was not a significant variable. A maximum OA concentration of 122.68 g/l could be obtained using the optimum levels of CAJ of 150.0 g/l, pH of 5.4, time of 7.31 days, NaNO3 of 2 g/l and methanol of 1% volume. The production of OA was found to increase from 106.75 to 122.68 g/l using the statistically design optimization. This study revealed that CAJ could serve as an inexpensive and abundant feedstock for fermentative OA production, the resulting model could be used in the design of a typical pilot plant for a scale up production. PMID:27441258

  20. Mechanisms of enhanced total organic carbon elimination from oxalic acid solutions by electro-peroxone process.

    PubMed

    Wang, Huijiao; Yuan, Shi; Zhan, Juhong; Wang, Yujue; Yu, Gang; Deng, Shubo; Huang, Jun; Wang, Bin

    2015-09-01

    Electro-peroxone (E-peroxone) is a novel electrocatalytic ozonation process that combines ozonation and electrolysis process to enhance pollutant degradation during water and wastewater treatment. This enhancement has been mainly attributed to several mechanisms that increase O3 transformation to ·OH in the E-peroxone system, e.g., electro-generation of H2O2 from O2 at a carbon-based cathode and its subsequent peroxone reaction with O3 to ·OH, electro-reduction of O3 to ·OH at the cathode, and O3 decomposition to ·OH at high local pH near the cathode. To get more insight how these mechanisms contribute respectively to the enhancement, this study investigated total organic carbon (TOC) elimination from oxalic acid (OA) solutions by the E-peroxone process. Results show that the E-peroxone process significantly increased TOC elimination rate by 10.2-12.5 times compared with the linear addition of the individual rates of corresponding ozonation and electrolysis process. Kinetic analyses reveal that the electrochemically-driven peroxone reaction is the most important mechanism for the enhanced TOC elimination rate, while the other mechanisms contribute minor to the enhancement by a factor of 1.6-2.5. The results indicate that proper selection of electrodes that can effectively produce H2O2 at the cathode is critical to maximize TOC elimination in the E-peroxone process.

  1. Mechanisms of enhanced total organic carbon elimination from oxalic acid solutions by electro-peroxone process.

    PubMed

    Wang, Huijiao; Yuan, Shi; Zhan, Juhong; Wang, Yujue; Yu, Gang; Deng, Shubo; Huang, Jun; Wang, Bin

    2015-09-01

    Electro-peroxone (E-peroxone) is a novel electrocatalytic ozonation process that combines ozonation and electrolysis process to enhance pollutant degradation during water and wastewater treatment. This enhancement has been mainly attributed to several mechanisms that increase O3 transformation to ·OH in the E-peroxone system, e.g., electro-generation of H2O2 from O2 at a carbon-based cathode and its subsequent peroxone reaction with O3 to ·OH, electro-reduction of O3 to ·OH at the cathode, and O3 decomposition to ·OH at high local pH near the cathode. To get more insight how these mechanisms contribute respectively to the enhancement, this study investigated total organic carbon (TOC) elimination from oxalic acid (OA) solutions by the E-peroxone process. Results show that the E-peroxone process significantly increased TOC elimination rate by 10.2-12.5 times compared with the linear addition of the individual rates of corresponding ozonation and electrolysis process. Kinetic analyses reveal that the electrochemically-driven peroxone reaction is the most important mechanism for the enhanced TOC elimination rate, while the other mechanisms contribute minor to the enhancement by a factor of 1.6-2.5. The results indicate that proper selection of electrodes that can effectively produce H2O2 at the cathode is critical to maximize TOC elimination in the E-peroxone process. PMID:25989593

  2. Asymmetric Mannich reaction between (S)-N-(tert-butanesulfinyl)-3,3,3-trifluoroacetaldimine and malonic acid derivatives. Stereodivergent synthesis of (R)- and (S)-3-amino-4,4,4-trifluorobutanoic acids.

    PubMed

    Shibata, Norio; Nishimine, Takayuki; Shibata, Naoyuki; Tokunaga, Etsuko; Kawada, Kosuke; Kagawa, Takumi; Aceña, José Luis; Sorochinsky, Alexander E; Soloshonok, Vadim A

    2014-03-01

    Inorganic as well as organic base catalysis was found to be effective for diastereoselective Mannich additions of malonic acid derivatives to (SS)-N-(tert-butanesulfinyl)-3,3,3-trifluoroacetaldimine. In the presence of catalytic amounts of inorganic bases, n-BuLi or DMAP, the reaction gives the corresponding (R,SS)-β-aminomalonates in good yield and with diastereoselectivity up to 9/1 dr. In contrast, phosphazene bases favour the formation of the (S,SS)-diastereomer with selectivities as high as 99/1. Simple choosing of an appropriate base catalyst for the Mannich addition reaction allowed us to obtain enantiomerically pure (R)- or (S)-configured 3-amino-4,4,4-trifluorobutanoic acids after hydrolysis and decarboxylation of the corresponding β-aminomalonates.

  3. 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.

  4. Evaluation of Hanford high level waste vitrification chemistry for an NCAW simulant -- FY 1994: Potential exothermic reactions in the presence of formic acid, glycolic acid, and oxalic acid

    SciTech Connect

    Sills, J.A.

    1995-07-01

    A potential for an uncontrollable exothermic reaction between nitrate and organic salts during preparation of a high level waste melter feed has been identified. In order to examine this potential more closely, the thermal behavior of simulated neutralized current acid waste (NCAW) treated with various organic reductants was studied. Differential scanning calorimetry (DSC) measurements were collected on simulated waste samples and their supernates treated with organics. Organic reductants used were formic acid, glycolic acid, and oxalic acid. For comparison, samples of untreated simulant and untreated simulant with added noble metals were tested. When heated, untreated simulant samples both with and without noble metals showed no exothermic behavior. All of the treated waste simulant samples showed exothermic behavior. Onset temperatures of exothermic reactions were 120 C to 210 C. Many onset temperatures, particularly those for formic acid treated samples, are well below 181 C, the estimated maximum steam coil temperature (considered to be a worst case maximum temperature for chemical process tank contents). The enthalpies of the reactions were {minus}180 {times} 10{sup {minus}3} J/Kg supernate ({minus}181 J/g) for the oxalic acid treated simulant supernate to {minus}1,150 {times} 10{sup {minus}3} J/Kg supernate ({minus}1,153 J/g) for the formic acid treated simulant supernate.

  5. Literature review for oxalate oxidation processes and plutonium oxalate solubility

    SciTech Connect

    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. 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.

  6. ACTUAL-WASTE TESTS OF ENHANCED CHEMICAL CLEANING FOR RETRIEVAL OF SRS HLW SLUDGE TANK HEELS AND DECOMPOSITION OF OXALIC ACID

    SciTech Connect

    Martino, C.; King, W.; Ketusky, E.

    2012-01-12

    Savannah River National Laboratory conducted a series of tests on the Enhanced Chemical Cleaning (ECC) process using actual Savannah River Site waste material from Tanks 5F and 12H. Testing involved sludge dissolution with 2 wt% oxalic acid, the decomposition of the oxalates by ozonolysis (with and without the aid of ultraviolet light), the evaporation of water from the product, and tracking the concentrations of key components throughout the process. During ECC actual waste testing, the process was successful in decomposing oxalate to below the target levels without causing substantial physical or chemical changes in the product sludge.

  7. Mimicking the biomolecular control of calcium oxalate monohydrate crystal growth: effect of contiguous glutamic acids.

    PubMed

    Grohe, Bernd; Hug, Susanna; Langdon, Aaron; Jalkanen, Jari; Rogers, Kem A; Goldberg, Harvey A; Karttunen, Mikko; Hunter, Graeme K

    2012-08-21

    Scanning confocal interference microscopy (SCIM) and molecular dynamics (MD) simulations were used to investigate the adsorption of the synthetic polypeptide poly(l-glutamic acid) (poly-glu) to calcium oxalate monohydrate (COM) crystals and its effect on COM formation. At low concentrations (1 μg/mL), poly-glu inhibits growth most effectively in ⟨001⟩ directions, indicating strong interactions of the polypeptide with {121} crystal faces. Growth in <010> directions was inhibited only marginally by 1 μg/mL poly-glu, while growth in <100> directions did not appear to be affected. This suggests that, at low concentrations, poly-glu inhibits lattice-ion addition to the faces of COM in the order {121} > {010} ≥ {100}. At high concentrations (6 μg/mL), poly-glu resulted in the formation of dumbbell-shaped crystals featuring concave troughs on the {100} faces. The effects on crystal growth indicate that, at high concentrations, poly-glu interacts with the faces of COM in the order {100} > {121} > {010}. This mirrors MD simulations, which predicted that poly-glu will adsorb to a {100} terrace plane (most calcium-rich) in preference to a {121} (oblique) riser plane but will adsorb to {121} riser plane in preference to an {010} terrace plane (least calcium-rich). The effects of different poly-glu concentration on COM growth (1-6 μg/mL) may be due to variations between the faces in terms of growth mechanism and/or (nano)roughness, which can affect surface energy. In addition, 1 μg/mL might not be adequate to reach the critical concentration for poly-glu to significantly pin step movement on {100} and {010} faces. Understanding the mechanisms involved in these processes is essential for the development of agents to reduce recurrence of kidney stone disease.

  8. Oxalic acid and diacylglycerol 36:3 are cross-species markers of sleep debt.

    PubMed

    Weljie, Aalim M; Meerlo, Peter; Goel, Namni; Sengupta, Arjun; Kayser, Matthew S; Abel, Ted; Birnbaum, Morris J; Dinges, David F; Sehgal, Amita

    2015-02-24

    Sleep is an essential biological process that is thought to have a critical role in metabolic regulation. In humans, reduced sleep duration has been associated with risk for metabolic disorders, including weight gain, diabetes, obesity, and cardiovascular disease. However, our understanding of the molecular mechanisms underlying effects of sleep loss is only in its nascent stages. In this study we used rat and human models to simulate modern-day conditions of restricted sleep and addressed cross-species consequences via comprehensive metabolite profiling. Serum from sleep-restricted rats was analyzed using polar and nonpolar methods in two independent datasets (n = 10 per study, 3,380 measured features, 407 identified). A total of 38 features were changed across independent experiments, with the majority classified as lipids (18 from 28 identified). In a parallel human study, 92 metabolites were identified as potentially significant, with the majority also classified as lipids (32 of 37 identified). Intriguingly, two metabolites, oxalic acid and diacylglycerol 36:3, were robustly and quantitatively reduced in both species following sleep restriction, and recovered to near baseline levels after sleep restriction (P < 0.05, false-discovery rate < 0.2). Elevated phospholipids were also noted after sleep restriction in both species, as well as metabolites associated with an oxidizing environment. In addition, polar metabolites reflective of neurotransmitters, vitamin B3, and gut metabolism were elevated in sleep-restricted humans. These results are consistent with induction of peroxisome proliferator-activated receptors and disruptions of the circadian clock. The findings provide a potential link between known pathologies of reduced sleep duration and metabolic dysfunction, and potential biomarkers for sleep loss.

  9. The chemistry of aminoguanidine derivatives - preparation, crystal structure, thermal properties, and molecular docking studies of aminoguanidinium salts of several carboxylic acids

    NASA Astrophysics Data System (ADS)

    Selvakumar, Rajendran; Geib, Steven J.; Muthu Sankar, Aathi; Premkumar, Thathan; Govindarajan, Subbaiah

    2015-11-01

    The reaction of aminoguanidine bicarbonate (Amg) with oxamic, oxalic, malonic and sulfoacetic acids yielded (AmgH)H2NOC-COO (1), OOC-CONHNHC(NH2)NH2 (2) (AmgH)HOOC-CH2-COO (3) and O3S-CH2-CONHNHC(NH2)NH2 (4), respectively. For the first time, we studied the salt-forming ability of aminoguanidine with several carboxylic acids, such as oxamic, oxalic, malonic and sulphoacetic acids. We also compared the structural and thermal properties of these salts. Oxamic and malonic acids form only mono-aminoguanidinium salts, whereas oxalic acid mainly forms di-aminoguanidinium oxalate. In addition, oxalic acid forms guanylhydrazido-oxalic acid which exists as zwitter ion. Unlike other acids, sulfoacetic acid readily forms only the zwitter ionic salts (2-guanylhydrazido-oxo-methanesulfonic acid) rather than the usual simple salt. This result may be a result of the highly acidic nature of the sulfonic group, which favors acid catalyzed condensation. More significantly, for the first time, the ability guanylhydrazido-oxalic acid (2) and 2-guanylhydrazido-oxo-methanesulfonic acid (4) to inhibit human butyrylcholinesterase (human BChE) receptor has been studied with a molecular docking approach. The binding of the compounds to human BChE was examined as it is crucial to understanding the biological significance of aminoguanidine derivatives. The compounds were identified and characterized by analytical, FT-IR spectroscopic and thermal studies. Furthermore, the structures of compounds 1, 2 and 4 were confirmed by single X-ray diffraction studies. Compounds 1 and 2 crystallized in a monoclinic crystal system with P21/c and Cc space groups, respectively, whereas compound 4 crystalized in an orthorhombic system with a Pbca space group. All the compounds (1-4) underwent endo- followed by exothermic decomposition in the temperature range from 130 to 600 °C to yield gaseous products.

  10. Enhanced efficiency of cadmium removal by Boehmeria nivea (L.) Gaud. in the presence of exogenous citric and oxalic acids.

    PubMed

    Li, Huaying; Liu, Yunguo; Zeng, Guangming; Zhou, Lu; Wang, Xin; Wang, Yaqin; Wang, Chunlin; Hu, Xinjiang; Xu, Weihua

    2014-12-01

    Boehmeria nivea (L.) Gaud. is a potential candidate for the remediation of Cd contaminated sites. The present investigation aims to explore Cd tolerance threshold and to quickly identify the role of exogenous organic acids in Cd uptake and abiotic metal stress damage. Elevated Cd levels (0-10mg/L) resulted in an obvious rise in Cd accumulation, ranging from 268.0 to 374.4 in root and 25.2 to 41.2mg/kg dry weight in shoot, respectively. Citric acid at 1.5 mmol/L significantly facilitated Cd uptake by 26.7% in root and by 1-fold in shoot, respectively. Cd translocation efficiency from root to shoot was improved by a maximum of 66.4% under 3 mmol/L of oxalic acid. Citric acid exhibited more prominent mitigating effect than oxalic acid due to its stronger ligand affinity for chelating with metal and avoiding the toxicity injury of free Cd ions more efficiently. The present work provides a potential strategy for efficient Cd remediation with B. nivea.

  11. Vapor pressures and lattice energies of oxalic acid, mesotartaric acid, phloroglucinol, myoinositol, and their hydrates

    NASA Astrophysics Data System (ADS)

    de Wit, H. G. M.; Bouwstra, J. A.; Blok, J. G.; de Kruif, C. G.

    1983-02-01

    In the present investigation, we report the enthalpy of dehydration and the enthalpy of sublimation of a number of organic hydrates and their anhydrous counterparts. These values are used to test the transferability of a set of atom-atom potential parameters, originally derived for carboxylic acids. The calculations showed that the parameter set was transferable to a fairly good degree.

  12. Postharvest treatments with salicylic acid, acetylsalicylic acid or oxalic acid delayed ripening and enhanced bioactive compounds and antioxidant capacity in sweet cherry.

    PubMed

    Valero, Daniel; Díaz-Mula, Huertas M; Zapata, Pedro Javier; Castillo, Salvador; Guillén, Fabián; Martínez-Romero, Domingo; Serrano, María

    2011-05-25

    Sweet cherry cultivars ('Cristalina' and 'Prime Giant') harvested at commercial ripening stage were treated with salicylic acid (SA), acetylsalicylic acid (ASA) or oxalic acid (OA) at 1 mM and then stored for 20 days under cold temperature. Results showed that all treatments delayed the postharvest ripening process, manifested by lower acidity, color changes and firmness losses, and maintained quality attributes for longer periods than controls. In addition, total phenolics, anthocyanins and antioxidant activity increased in untreated fruit during the first 10 days of storage and then decreased, while in fruits of all treatments, these parameters increased continuously during storage without significant differences among treatments. Thus, postharvest treatments with natural compounds, such as SA, ASA or OA, could be innovative tools to extend the storability of sweet cherry with higher content of bioactive compounds and antioxidant activity as compared with control fruits. PMID:21506518

  13. Postharvest treatments with salicylic acid, acetylsalicylic acid or oxalic acid delayed ripening and enhanced bioactive compounds and antioxidant capacity in sweet cherry.

    PubMed

    Valero, Daniel; Díaz-Mula, Huertas M; Zapata, Pedro Javier; Castillo, Salvador; Guillén, Fabián; Martínez-Romero, Domingo; Serrano, María

    2011-05-25

    Sweet cherry cultivars ('Cristalina' and 'Prime Giant') harvested at commercial ripening stage were treated with salicylic acid (SA), acetylsalicylic acid (ASA) or oxalic acid (OA) at 1 mM and then stored for 20 days under cold temperature. Results showed that all treatments delayed the postharvest ripening process, manifested by lower acidity, color changes and firmness losses, and maintained quality attributes for longer periods than controls. In addition, total phenolics, anthocyanins and antioxidant activity increased in untreated fruit during the first 10 days of storage and then decreased, while in fruits of all treatments, these parameters increased continuously during storage without significant differences among treatments. Thus, postharvest treatments with natural compounds, such as SA, ASA or OA, could be innovative tools to extend the storability of sweet cherry with higher content of bioactive compounds and antioxidant activity as compared with control fruits.

  14. Thermodynamics of the Complexation of Uranium(VI) by oxalate in aqueous solution at 10-70oC

    SciTech Connect

    Di Bernardo, Plinio; Zanonato, Pier Luigi; Tian, Guoxin; Tolazzi, Marilena; Rao, Linfeng

    2009-03-31

    The protonation reactions of oxalate (ox) and the complex formation of uranium(VI) with oxalate in 1.05 mol kg{sup -1} NaClO{sub 4} were studied at variable temperatures (10-70 C). Three U(VI)/ox complexes (UO{sub 2}ox{sub j}{sup (2-2j){sup +}} with j = 1, 2, 3) were identified in this temperature range. The formation constants and the molar enthalpies of complexation were determined by spectrophotometry and calorimetry. The complexation of uranium(VI) with oxalate ion is exothermic at lower temperatures (10-40 C) and becomes endothermic at higher temperatures (55-70 C). In spite of this, the free energy of complexation becomes more negative at higher temperatures due to increasingly more positive entropy of complexation that exceeds the increase of the enthalpy of complexation. The thermodynamic parameters at different temperatures, in conjunction with the literature data for other dicarboxylic acids, provide insight into the relative strength of U(VI) complexes with a series of dicarboxylic acids (oxalic, malonic and oxydiacetic) and rationalization for the highest stability of U(VI)/oxalate complexes in the series. The data reported in this study are of importance in predicting the migration of uranium(VI) in geological environments in the case of failure of the engineering barriers which protect waste repositories.

  15. Characteristics and sources of formic, acetic and oxalic acids in PM 2.5 and PM 10 aerosols in Beijing, China

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Zhuang, Guoshun; Chen, Shuang; An, Zhisheng; Zheng, Aihua

    2007-04-01

    Chemistry of formic, acetic and oxalic acids was studied at four sites representing the urban and rural conditions in Beijing from March 2002 to October 2003. The investigation was based on the PM 2.5 and PM 10 aerosols collected with virtual samplers. The total concentrations of these carboxylic acids averaged at 541 ng m - 3 in PM 2.5 and 615 ng m - 3 in PM 10, contributing 0.4% and 0.3% to the total mass of the aerosol, respectively. Oxalic acid was the most abundant carboxylic acids in aerosols. Formic and acetic acids displayed different seasonal variations (formic: spring < summer < autumn < winter; acetic: spring > summer > autumn > winter), and the variations of these acids were consistent among different sites in urban area. Formic and oxalic acids had a diurnal variation of nighttime < daytime. Formic and acetic acids had mass both in the fine and in the coarse modes, while oxalic acid predominated in the fine mode. The coarse mode fraction of these acids was elevated in summer. The traffic/dust/soil/vegetation emissions, coal/waste/biomass burnings, cooking and secondary formation from anthropogenic or natural gas-phase precursors could be the major sources of these acids. Acetic-to-formic acid ratio (A/F) was used to distinguish the primary sources and the secondary sources, and it indicated that the contribution of the primary sources was higher at rural site than at urban sites. A new method was developed to study the contribution of the biomass burning to these acids, which was estimated to be 30-60% for formic and oxalic acids in aerosols.

  16. LITERATURE REVIEW FOR OXALATE OXIDATION PROCESSES AND PLUTONIUM OXALATE SOLUBILITY

    SciTech Connect

    Nash, C.

    2012-02-03

    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. 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. H Canyon plans to commence conversion of plutonium metal to low-fired plutonium oxide in 2012 for eventual use in the Mixed Oxide Fuel (MOX) Facility. The flowsheet includes sequential operations of metal dissolution, ion exchange, elution, oxalate precipitation, filtration, and calcination. All processes beyond dissolution will occur in HB-Line. The filtration step produces an aqueous filtrate that may have as much as 4 M nitric acid and 0.15 M oxalate. The oxalate needs to be removed from the stream to prevent possible downstream precipitation of residual plutonium when the solution is processed in H Canyon. In addition, sending the oxalate to the waste tank farm is undesirable. This report addresses the processing options for destroying the oxalate in existing H Canyon equipment.

  17. Pre-harvest application of oxalic acid increases quality and resistance to Penicillium expansum in kiwifruit during postharvest storage.

    PubMed

    Zhu, Yuyan; Yu, Jie; Brecht, Jeffrey K; Jiang, Tianjia; Zheng, Xiaolin

    2016-01-01

    Kiwifruit (Actinidia deliciosa cv. Bruno) fruits were sprayed with 5mM oxalic acid (OA) at 130, 137, and 144 days after full blossom, and then harvested at commercial maturity [soluble solid content (SSC) around 10.0%] and stored at room temperature (20 ± 1 °C). Pre-harvest application of OA led to fruit with higher ascorbic acid content at harvest, slowed the decreases in fruit firmness and ascorbic acid content and increase in SSC during storage, and also decreased the natural disease incidence, lesion diameter, and patulin accumulation in fruit inoculated with Penicillium expansum, indicating that the OA treatment increased quality and induced disease resistance in kiwifruit. It was suggested that the increase in activities of defense-related enzymes and in levels of substances related to disease resistance might collectively contribute to resistance in kiwifruit against fungi such as P. expansum in storage. PMID:26213007

  18. Pre-harvest application of oxalic acid increases quality and resistance to Penicillium expansum in kiwifruit during postharvest storage.

    PubMed

    Zhu, Yuyan; Yu, Jie; Brecht, Jeffrey K; Jiang, Tianjia; Zheng, Xiaolin

    2016-01-01

    Kiwifruit (Actinidia deliciosa cv. Bruno) fruits were sprayed with 5mM oxalic acid (OA) at 130, 137, and 144 days after full blossom, and then harvested at commercial maturity [soluble solid content (SSC) around 10.0%] and stored at room temperature (20 ± 1 °C). Pre-harvest application of OA led to fruit with higher ascorbic acid content at harvest, slowed the decreases in fruit firmness and ascorbic acid content and increase in SSC during storage, and also decreased the natural disease incidence, lesion diameter, and patulin accumulation in fruit inoculated with Penicillium expansum, indicating that the OA treatment increased quality and induced disease resistance in kiwifruit. It was suggested that the increase in activities of defense-related enzymes and in levels of substances related to disease resistance might collectively contribute to resistance in kiwifruit against fungi such as P. expansum in storage.

  19. Biocontrol agents-mediated suppression of oxalic acid induced cell death during Sclerotinia sclerotiorum-pea interaction.

    PubMed

    Jain, Akansha; Singh, Akanksha; Singh, Surendra; Sarma, Birinchi Kumar; Singh, Harikesh Bahadur

    2015-05-01

    Oxalic acid (OA) is an important pathogenic factor during early Sclerotinia sclerotiorum-host interaction and might work by reducing hydrogen peroxide production (H2 O2 ). In the present investigation, oxalic acid-induced cell death in pea was studied. Pea plants treated with biocontrol agents (BCAs) viz., Pseudomonas aeruginosa PJHU15, Bacillus subtilis BHHU100, and Trichoderma harzianum TNHU27 either singly and/or in consortium acted on S. sclerotiorum indirectly by enabling plants to inhibit the OA-mediated suppression of oxidative burst via induction of H2 O2 . Our results showed that BCA treated plants upon treatment with culture filtrate of the pathogen, conferred the resistance via. significantly decreasing relative cell death of pea against S. sclerotiorum compared to control plants without BCA treatment but treated with the culture filtrate of the pathogen. The results obtained from the present study indicate that the microbes especially in consortia play significant role in protection against S. sclerotiorum by modulating oxidative burst and partially enhancing tolerance by increasing the H2 O2 generation, which is otherwise suppressed by OA produced by the pathogen.

  20. Development and validation of a simple determination of urine metabolites (oxalate, citrate, uric acid and creatinine) by capillary zone electrophoresis.

    PubMed

    Muñoz, Jose A; López-Mesas, Montserrat; Valiente, Manuel

    2010-04-15

    Oxalate, citrate, uric acid and creatinine are important urine markers for the evaluation and treatment of urolithiasic patients. They have been traditionally analysed by enzymatic and chromatographic techniques which present practical drawbacks, mainly in the sample pre-treatment step. The purpose of this study was to evaluate those markers in urine samples, by an easy multi-analyte assay using capillary zone electrophoresis. The four urine metabolites were determined, at 25 degrees C, by using a 50 cm x 75 microm capillary in 50 mmol l(-1) phosphate buffer (pH 6.5), at constant voltage of -30 kV and UV detection at 195 nm (for oxalate and citrate) or 30 kV and 234 nm (for creatinine and uric acid). The sample pre-treatment was minimum, 5- and 20-fold dilution of the urine sample and acidification to pH 3-4. Validation parameters (linear range, sensitivity, accuracy, precision and detection limits) were statistically comparable to those obtained with the official methods normally used in the clinical practice. The effect of freezing as a conservation method of urine samples is also discussed in terms of recoveries of the analytes. The analytical method developed is highly useful as a diagnostic tool for detecting metabolic renal disorders due to its simplicity, time consuming, easy automation, cost efficiency and analytical effectiveness, accomplishing with the clinical requirements.

  1. Degradation of oxalic acid by the mycoparasite Coniothyrium minitans plays an important role in interacting with Sclerotinia sclerotiorum.

    PubMed

    Zeng, Li-Mei; Zhang, Jing; Han, Yong-Chao; Yang, Long; Wu, Ming-de; Jiang, Dao-Hong; Chen, Weidong; Li, Guo-Qing

    2014-08-01

    Coniothyrium minitans (Cm) is a mycoparasite of the phytopathogenic fungus Sclerotinia sclerotiorum (Ss). Ss produces a virulence factor oxalic acid (OA) which is toxic to plants and also to Cm, and Cm detoxifies OA by degradation. In this study, two oxalate decarboxylase genes, Cmoxdc1 and Cmoxdc2, were cloned from Cm strain Chy-1. OA and low pH induced expression of Cmoxdc1, but not Cmoxdc2. Cmoxdc1 was partially responsible for OA degradation, whereas Cmoxdc2 had no effect on OA degradation. Disruption of Cmoxdc1 in Cm reduced its ability to infect Ss in dual cultures where OA accumulated. Compared with Chy-1, the Cmoxdc1-disrupted mutants had reduced expression levels of two mycoparasitism-related genes chitinase (Cmch1) and β-1,3-glucanase (Cmg1), and had no detectable activity of extracellular proteases in the presence of OA. On the other hand, the cultural filtrates of the Cmoxdc1-disrupted mutants in OA-amended media showed enhanced antifungal activity, possibly because of increased production of antifungal substances under acidic pH condition resulted from reduced Cmoxdc1-mediated OA degradation. This study provides direct genetic evidence of OA degradation regulating mycoparasitism and antibiosis of Cm against Ss, and sheds light on the sophisticated strategies of Cm in interacting with metabolically active mycelia and dormant sclerotia of Ss. PMID:24467446

  2. 3-Ketoesters by Malonic Synthesis.

    ERIC Educational Resources Information Center

    Pollet, Patrick L.

    1983-01-01

    Discusses the acylation version of malonic synthesis of three-ketoesters. Includes advantages of this method over other methodologies including a final selective removal of the "activating" ester function in such mild conditions that most of the organic functions may survive. (JN)

  3. Mode of Action: Oxalate Crystal-Induced Renal Tubule Degeneration and Glycolic Acid-Induced Dysmorphogenesis—Renal and Developmental Effects of Ethylene Glycol

    SciTech Connect

    Corley, Rick A.; Meek, M E.; Carney, E W.

    2005-10-01

    Ethylene glycol can cause both renal and developmental toxicity, with metabolism playing a key role in the mode of action (MOA) for each form of toxicity. Renal toxicity is ascribed to the terminal metabolite oxalic acid, which precipitates in the kidney in the form of calcium oxalate crystals and is believed to cause physical damage to the renal tubules. The human relevance of the renal toxicity of ethylene glycol is indicated by the similarity between animals and humans of metabolic pathways, the observation of renal oxalate crystals in toxicity studies in experimental animals and human poisonings, and cases of human kidney and bladder stones related to dietary oxalates and oxalate precursors. High-dose gavage exposures to ethylene glycol also cause axial skeletal defects in rodents (but not rabbits), with the intermediary metabolite, glycolic acid, identified as the causative agent. However, the mechanism by which glycolic acid perturbs development has not been investigated sufficiently to develop a plausible hypothesis of mode of action, nor have any cases of ethylene glycol-induced developmental effects been reported in humans. Given this, and the variations in sensitivity between animal species in response, the relevance to humans of ethylene glycol-induced developmental toxicity in animals is unknown at this time.

  4. In vivo measurements of changes in pH triggered by oxalic acid in leaf tissue of transgenic oilseed rape.

    PubMed

    Zou, Qiu-Ju; Liu, Sheng-Yi; Dong, Xu-Yan; Bi, Yan-Hua; Cao, Yuan-Cheng; Xu, Qiao; Zhao, Yuan-Di; Chen, Hong

    2007-01-01

    Oxalic acid (OA), a non-host-specific toxin secreted by Sclerotinia sclerotiorum during pathogenesis, has been demonstrated to be a major phytotoxic and pathogenic factor. Oxalate oxidase (OXO) is an enzyme associated with the detoxification of OA, and hence the introduction of an OXO gene into oilseed rape (Brassica napus L.) to break down OA may be an alternative way of increasing the resistance of the plant to Sclerotinia sclerotiorum. In order to investigate the activation of OXO in transgenic oilseed rape, a convenient and accessible method was used to monitor changes in pH in response to stress induced by OA. The pH sensor, a platinum microcylinder electrode modified using polyaniline film, exhibited a linear response within the pH range from 3 to 7, with a Nernst response slope of 70 mV/pH at room temperature. The linear correlation coefficient was 0.9979. Changes induced by OA in the pH values of leaf tissue of different oilseed rape species from Brassica napus L. were monitored in real time in vivo using this electrode. The results clearly showed that the transgenic oilseed rape was more resistant to OA than non-transgenic oilseed rape.

  5. Oxaloacetate acetylhydrolase gene mutants of Sclerotinia sclerotiorum do not accumulate oxalic acid, but do produce limited lesions on host plants.

    PubMed

    Liang, Xiaofei; Liberti, Daniele; Li, Moyi; Kim, Young-Tae; Hutchens, Andrew; Wilson, Ron; Rollins, Jeffrey A

    2015-08-01

    The oxaloacetate acetylhydrolase (OAH, EC 3.7.1.1)-encoding gene Ss-oah1 was cloned and functionally characterized from Sclerotinia sclerotiorum. Ss-oah1 transcript accumulation mirrored oxalic acid (OA) accumulation with neutral pH induction dependent on the pH-responsive transcriptional regulator Ss-Pac1. Unlike previously characterized ultraviolet (UV)-induced oxalate-deficient mutants ('A' mutants) which retain the capacity to accumulate OA, gene deletion Δss-oah1 mutants did not accumulate OA in culture or during plant infection. This defect in OA accumulation was fully restored on reintroduction of the wild-type (WT) Ss-oah1 gene. The Δss-oah1 mutants were also deficient in compound appressorium and sclerotium development and exhibited a severe radial growth defect on medium buffered at neutral pH. On a variety of plant hosts, the Δss-oah1 mutants established very restricted lesions in which the infectious hyphae gradually lost viability. Cytological comparisons of WT and Δss-oah1 infections revealed low and no OA accumulation, respectively, in subcuticular hyphae. Both WT and mutant hyphae exhibited a transient association with viable host epidermal cells at the infection front. In summary, our experimental data establish a critical requirement for OAH activity in S. sclerotiorum OA biogenesis and pathogenesis, but also suggest that factors independent of OA contribute to the establishment of primary lesions. PMID:25285668

  6. A comparative density functional theory study of electronic structure and optical properties of γ-aminobutyric acid and its cocrystals with oxalic and benzoic acid

    NASA Astrophysics Data System (ADS)

    da Silva Filho, J. G.; Freire, V. N.; Caetano, E. W. S.; Ladeira, L. O.; Fulco, U. L.; Albuquerque, E. L.

    2013-11-01

    In this letter, we study the electronic structure and optical properties of the active medicinal component γ-aminobutyric acid (GABA) and its cocrystals with oxalic (OXA) and benzoic (BZA) acid by means of the density functional theory formalism. It is shown that the cocrystallization strongly weakens the zwitterionic character of the GABA molecule leading to striking differences among the electronic band structures and optical absorption spectra of the GABA crystal and GABA:OXA, GABA:BZA cocrystals, originating from distinct sets of hydrogen bonds. Calculated band widths and Δ-sol band gap estimates indicate that both GABA and GABA:OXA, GABA:BZA cocrystals are indirect gap insulators.

  7. 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.

  8. Actual-Waste Tests of Enhanced Chemical Cleaning for Retrieval of SRS HLW Sludge Tank Heels and Decomposition of Oxalic Acid - 12256

    SciTech Connect

    Martino, Christopher J.; King, William D.; Ketusky, Edward T.

    2012-07-01

    Savannah River National Laboratory conducted a series of tests on the Enhanced Chemical Cleaning (ECC) process using actual Savannah River Site waste material from Tanks 5F and 12H. Testing involved sludge dissolution with 2 wt% oxalic acid, the decomposition of the oxalates by ozonolysis (with and without the aid of ultraviolet light), the evaporation of water from the product, and tracking the concentrations of key components throughout the process. During ECC actual waste testing, the process was successful in decomposing oxalate to below the target levels without causing substantial physical or chemical changes in the product sludge. During ECC actual waste testing, the introduction of ozone was successful in decomposing oxalate to below the target levels. This testing did not identify physical or chemical changes in the ECC product sludge that would impact downstream processing. The results from these tests confirm observations made by AREVA NP during larger scale testing with waste simulants. This testing, however, had a decreased utilization of ozone, requiring approximately 5 moles of ozone per mole of oxalate decomposed. Decomposition of oxalates in sludge dissolved in 2 wt% OA to levels near 100 ppm oxalate using ECC process conditions required 8 to 12.5 hours without the aid of UV light and 4.5 to 8 hours with the aid of UV light. The pH and ORP were tracked during decomposition testing. Sludge components were tracked during OA decomposition, showing that most components have the highest soluble levels in the initial dissolved sludge and early decomposition samples and exhibit lower soluble levels as OA decomposition progresses. The Deposition Tank storage conditions that included pH adjustment to approximately 1 M free hydroxide tended to bring the soluble concentrations in the ECC product to nearly the same level for each test regardless of storage time, storage temperature, and contact with other tank sludge material. (authors)

  9. Oxalic-acid leaching of rock, soil, and stream-sediment samples as an anomaly-accentuated technique

    USGS Publications Warehouse

    Alminas, Henry V.; Mosier, Elwin L.

    1976-01-01

    In many instances total-rock and sieved-soil and stream-sediment samples lack the sensitivity and contrast required for reconnaissance exploration and necessary in the search for blind ore deposits. Heavy-mineral concentrates incorporate the required sensitivity and contrast but are overly expensive for two reasons: time-consuming sample preparation is required to obtain them, and they cannot be easily derived from all bulk-sample types. Trace-metal-content comparisons of the oxalic-acid-leachable portions with heavy-mineral concentrates show that the leachates are equal to the heavy-mineral concentrates in sensitivity and contrast. Simplicity of preparation and the resultant cost savings are additional advantages of this proposed method.

  10. A new approach to the decontamination of asbestos-polluted waters by treatment with oxalic acid under power ultrasound.

    PubMed

    Turci, Francesco; Tomatis, Maura; Mantegna, Stefano; Cravotto, Giancarlo; Fubini, Bice

    2008-04-01

    A suspension of chrysotile asbestos fibres in aqueous 0.5M oxalic acid was subjected to power ultrasound with the aim to disrupt and detoxify the mineral by the leaching action of oxalic acid on its structural cations acting simultaneously with a vigorous acoustic cavitation. Sonication was performed in a "cavitating tube", a vertical hollow vibrating cylinder made of titanium, operating at 19.2 kHz and 150 W. Treatment lasted from 2.5 to 21 h. Scanning electron microscopy (SEM) showed that the joint action of the chelating agent and ultrasound (though not of either when applied independently) mostly converted asbestos fibres into micrometric aggregates and nano-sized debris, whose morphology totally differed from asbestos fibres. When treated suspensions were filtered through CA membranes (pore size 0.20 microm), more than half of the asbestos went through the filter because it had either been brought in solution or dispersed in the form of extremely small particles. Most of the structural metal ions were brought into solution (ICP-AES). After the treatment the BET surface area of the recovered solid was tenfold greater than the original. The crystalline fraction of residual solids, though resembling the original sample in XRD, was shown by micro-Raman spectra to be made of antigorite, a polymorph form of serpentine. Furthermore, as the length of these antigorite fibrils lay outside the fibre range rated as a health hazard under worldwide regulations, our procedure can be employed for the decontamination of chrysotile-polluted waters and sediments.

  11. Automated homogeneous oxalate precipitation of Pu(III)

    SciTech Connect

    Yarbro, S.L.; Schreiber, S.B.; Dunn, S.L.; Mills, C.W.

    1990-01-01

    Homogeneous oxalate precipitation using diethyl oxalate was compared to precipitating Pu(III) oxalate with solid oxalic acid. The diethyl oxalate technique at 75{degree}C is better because it gives 50% less plutonium in the filtrate with a reasonable filtering time. Also, the procedure for the homogeneous precipitation is easier to automate because the liquid diethyl oxalate is simpler to introduce into the precipitator than solid oxalic acid. It also provides flexibility because the hydrolysis rate and therefore the precipitation rate can be controlled by varying the temperature. 5 refs., 3 figs., 3 tabs.

  12. Preharvest application of oxalic acid increased fruit size, bioactive compounds, and antioxidant capacity in sweet cherry cultivars (Prunus avium L.).

    PubMed

    Martínez-Esplá, Alejandra; Zapata, Pedro Javier; Valero, Daniel; García-Viguera, Cristina; Castillo, Salvador; Serrano, María

    2014-04-16

    Trees of 'Sweet Heart' and 'Sweet Late' sweet cherry cultivars (Prunus avium L.) were treated with oxalic acid (OA) at 0.5, 1.0, and 2.0 mM at 98, 112, and 126 days after full blossom. Results showed that all treatments increased fruit size at harvest, manifested by higher fruit volume and weight in cherries from treated trees than from controls, the higher effect being found with 2.0 mM OA (18 and 30% higher weight for 'Sweet Heart' and 'Sweet Late', respectively). Other quality parameters, such as color and firmness, were also increased by OA treatments, although no significant differences were found in total soluble solids or total acidity, showing that OA treatments did not affect the on-tree ripening process of sweet cherry. However, the increases in total anthocyanins, total phenolics, and antioxidant activity associated with the ripening process were higher in treated than in control cherries, leading to fruit with high bioactive compounds and antioxidant potential at commercial harvest (≅45% more anthocyanins and ≅20% more total phenolics). In addition, individual anthocyanins, flavonols, and chlorogenic acid derivatives were also increased by OA treatment. Thus, OA preharvest treatments could be an efficient and natural way to increase the quality and functional properties of sweet cherries. PMID:24684635

  13. Chrysotile asbestos detoxification with a combined treatment of oxalic acid and silicates producing amorphous silica and biomaterial.

    PubMed

    Valouma, Aikaterini; Verganelaki, Anastasia; Maravelaki-Kalaitzaki, Pagona; Gidarakos, Evangelos

    2016-03-15

    This study was primarily imposed by the ever increasing need for detoxification of asbestos and asbestos containing materials (ACM), with potential application onsite. The present work investigates potential detoxification of pure chrysotile (Chr) asbestos via a combined treatment of oxalic acid dihydrate (Oxac) (Η2C2Ο4·2Η2Ο) with silicates, such as tetraethoxysilane (TEOS) (SiH20C8O4) and pure water glass (WG) (potassium silicate) (K2SiO3). These reagents used in the experimental procedure, do not cause adverse effects on the environment and are cost effective. The results of FTIR, XRD, optical and scanning microscopy coupled with EDS analyses indicated that all of the applied treatments destructed the Chr structure and yielded silica of amorphous phase and the biomaterial glushinskite from the Oxac reacted with brucite [Mg(OH)2] layer. Each of the proposed formulations can be applied for the detoxification of asbestos, according to priorities related to the specific products of the recovery treatment. Therefore, Oxac acid leaching followed by the TEOS addition is preferred in cases of glushinskite recovery; TEOS treatment of asbestos with subsequent Oxac addition produced amorphous silica production; finally Oxac acid leaching followed by WG encapsulated the asbestos fibers and can be used in cases of onsite asbestos and ACM detoxification.

  14. Aluminium resistance requires resistance to acid stress: a case study with spinach that exudes oxalate rapidly when exposed to Al stress.

    PubMed

    Yang, Jian Li; Zheng, Shao Jian; He, Yun Feng; Matsumoto, Hideaki

    2005-04-01

    Spinach is a vegetable with a high oxalate concentration in its tissues. Oxalate efflux from spinach (Spinacia oleracea L. cv. Quanneng) roots was rapidly stimulated (within 30 min) by aluminium (Al) treatment. The efflux was constant within 6 h, but increased with increasing Al concentration. The efflux was confined to the root tip (0-5 mm), which showed a 5-fold greater efflux than the root zone distal to the tip (5-10 mm). Oxalate efflux could not be triggered by treatment with the trivalent cation lanthanum or by phosphorus deficiency, indicating that the efflux was specific to the Al treatment. All this evidence suggested that spinach possesses Al-resistance mechanisms. However, spinach was found to be as sensitive to Al toxicity as the Al-sensitive wheat line ES8, which had no Al-dependent organic acids efflux. The Al accumulated in the apical 5 mm of the roots of spinach which was also similar to that in the Al-sensitive wheat after 24 h treatment with 50 microM AlCl(3), indicating a non-exclusion mechanism. In addition, root elongation in spinach was significantly inhibited at pH 4.5, compared with that at pH 6.5. Based on this evidence, it is concluded that the sensitivity to acid stress in spinach could mask the potential role for oxalate to protect the plant roots from Al toxicity.

  15. 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.

  16. Synthesis of nanomagnetic fluids and their UV spectrophotometric response with aliphatic organic acids and 1st tier dendrimers

    NASA Astrophysics Data System (ADS)

    Pandya, Shivani R.; Singh, Man

    2016-04-01

    Synthesis of Magnetic nanoparticles were made using coprecipitation method on mixing Fe+3 and Fe+2 in 2:1 ratio with aqueous 8M NaOH which on heating at 90°C for 2 h has yielded 85% magnetic (Fe3O4) nanoparticles (MNPs), characterized by XRD, VSM, SEM, and HR-TEM. The formic acid (FA), oxalic acid (OA) and citric acid (CA), the series of aliphatic organic acids along with Trimesoyl 1, 3, 5 tridimethyl malonate (TTDMM), trimesoyl 1, 3, 5 tridiethyl malonate (TTDEM), trimesoyl 1, 3, 5 tridipropyl malonate (TTDPM), trimesoyl 1, 3, 5 tridibutyl malonate (TTDBM) and trimesoyl 1, 3, 5 tridihexyl malonate (TTDHM) 1st tier dendrimers were used separately for preparing nanomagnetic fluid. From 25 to 150 µM MNPs at an interval of 25 µM were dispersed in 150 µM of acids and dendrimers separately with DMSO. UV-VIS spectrophotometry showed a maximum MNPs dispersion with TTDMM against others and found to be most stable nanomagnetic fluid on account of capping type mechanism of acids.

  17. Hanford waste vitrification plant hydrogen generation study: Preliminary evaluation of alternatives to formic acid

    SciTech Connect

    King, R.B.; Bhattacharyya, N.K.; Kumar, V.

    1996-02-01

    Oxalic, glyoxylic, glycolic, malonic, pyruvic, lactic, levulinic, and citric acids as well as glycine have been evaluated as possible substitutes for formic acid in the preparation of feed for the Hanford waste vitrification plant using a non-radioactive feed stimulant UGA-12M1 containing substantial amounts of aluminum and iron oxides as well as nitrate and nitrite at 90C in the presence of hydrated rhodium trichloride. Unlike formic acid none of these carboxylic acids liberate hydrogen under these conditions and only malonic and citric acids form ammonia. Glyoxylic, glycolic, malonic, pyruvic, lactic, levulinic, and citric acids all appear to have significant reducing properties under the reaction conditions of interest as indicated by the observation of appreciable amounts of N{sub 2}O as a reduction product of,nitrite or, less likely, nitrate at 90C. Glyoxylic, pyruvic, and malonic acids all appear to be unstable towards decarboxylation at 90C in the presence of Al(OH){sub 3}. Among the carboxylic acids investigated in this study the {alpha}-hydroxycarboxylic acids glycolic and lactic acids appear to be the most interesting potential substitutes for formic acid in the feed preparation for the vitrification plant because of their failure to produce hydrogen or ammonia or to undergo decarboxylation under the reaction conditions although they exhibit some reducing properties in feed stimulant experiments.

  18. Effect of organic and conventional cropping systems on ascorbic acid, vitamin C, flavonoids, nitrate, and oxalate in 27 varieties of spinach (Spinacia oleracea L.).

    PubMed

    Koh, Eunmi; Charoenprasert, Suthawan; Mitchell, Alyson E

    2012-03-28

    This study was undertaken to compare the levels of ascorbic acid, vitamin C, flavonoids, nitrate, and oxalate in 27 spinach varieties grown in certified organic and conventional cropping systems. Liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-(ESI)MS/MS) of methanolic extracts of spinach demonstrated 17 flavonoids, including glucuronides and acylated di- and triglycosides of methylated and methylenedioxyderivatives of 6-oxygenated flavonoids. The mean levels of ascorbic acid and flavonoids were significantly (p < 0.001) higher in the organically grown [40.48 ± 6.16 and 2.83 ± 0.03 mg/kg of fresh weight (FW)] spinach compared to the conventionally grown spinach (25.75 ± 6.12 and 2.27 ± 0.02 mg/kg of FW). Conversely, the mean levels of nitrate were significantly (p < 0.001) higher in the conventionally grown spinach compared to the organically grown spinach. No significant effects were observed in the oxalate content of spinach from either production system. The levels of nitrate correlated negatively with those of ascorbic acid, vitamin C, and total flavonoids and showed a positive correlation with the oxalate content. These results suggest that organic cropping systems result in spinach with lower levels of nitrates and higher levels of flavonoids and ascorbic acid.

  19. An improved thermodynamic model for the complexation of trivalent actinides and lanthanide with oxalic acid valid to high ionic strength.

    DOE PAGES

    Xiong, Yongliang; Thakur, Punam; Borkowski, Marian

    2015-07-30

    The dissociation constants of oxalic acid (Ox), and the stability constants of Am3+, Cm3+ and Eu3+ with Ox2– have been determined at 25 °C, over a range of concentration varying from 0.1 to 6.60 m NaClO4 using potentiometric titration and extraction techniques, respectively. The experimental data support the formation of complexes, M(Ox)n3 – 2n, where (M = Am3+, Cm3+ and Eu3+ and n = 1 and 2). The dissociation constant and the stability constant values measured as a function of NaClO4 concentration were used to estimate the Pitzer parameters for the respective interactions of Am3+, Cm3+ and Eu3+ with Ox.more » Furthermore, the stability constants data of Am3+ –Ox measured in NaClO4 and in NaCl solutions from the literature were simultaneously fitted in order to refine the existing actinide–oxalate complexation model that can be used universally in the safety assessment of radioactive waste disposal. The thermodynamic stability constant: log β0101 = 6.30 ± 0.06 and log β0102 = 10.84 ± 0.06 for Am3+ was obtained by simultaneously fitting data in NaCl and NaClO4 media. Additionally, log β0101 = 6.72 ± 0.08 and log β0102 = 11.05 ± 0.09 for the Cm3+ and log β0101 = 6.67 ± 0.08 and log β0102 = 11.15 ± 0.09 for the Eu3+ were calculated by extrapolation of data to zero ionic strength in NaClO4 medium only. For all stability constants, the Pitzer model gives an excellent representation of the data using interaction parameters β(0), β(1), and CΦ determined in this work. The thermodynamic model developed in this work will be useful in accurately modeling the potential solubility of trivalent actinides and early lanthanides to ionic strength of 6.60 m in low temperature environments in the presence of Ox. Furthermore, the work is also applicable to the accurate modeling transport of rare earth elements in various environments under the surface conditions.« less

  20. Short term tolvaptan increases water intake and effectively decreases urinary calcium oxalate, calcium phosphate, and uric acid supersaturations

    PubMed Central

    Cheungpasitporn, Wisit; Erickson, Stephen B.; Rule, Andrew D.; Enders, Felicity; Lieske, John C.

    2016-01-01

    Purpose Many patients cannot effectively increase water intake and urine volume to prevent urinary stones. Tolvaptan, a V2 receptor antagonist, blocks water reabsorption in the collecting duct and should reduce urinary supersaturation (SS) of stone forming solutes, but this has never been proven. Materials and Methods We conducted a double blind, randomized, placebo-controlled, crossover study in 21 adult calcium urinary stone formers stratified as majority calcium oxalate(CaOx, n=10) or calcium phosphate(CaP, n=11). Patients received tolvaptan 45 mg/day or placebo for 1 week, followed by a washout week and crossover to tolvaptan or placebo for week 3. A 24h urines was collected at the end of weeks 1 and 3. Results Tolvaptan vs. placebo decreased urinary osmolality (204±96 vs 529±213 mOsm/kg, P<0.001) and increased urinary volume (4.8±2.9 vs 1.8±0.9 L, P<0.001). The majority of urinary solute excretion rates including sodium and calcium did not significantly change, although oxalate secretion slightly increased (23±8 to 15±8 mg/24h, P = 0.009). Urinary CaOx SS (−0.01±1.14 vs 0.95±0.87 DG, P<0.001), CaP SS (−1.66±1.17 vs −0.13±1.02 DG, P<0.001) and Uric Acid SS (−2.05±4.05 vs −5.24±3.12 DG, P=0.04) all dramatically decreased. Effects did not differ between CaOx and CaP groups (P>0.05 for all interactions). Conclusions Tolvaptan increases urine volume and decreases urinary SS in calcium stone formers. Further study is needed to determine if long term use of V2 receptor antagonists results in fewer stone events. PMID:26598423

  1. The hygroscopic properties of dicarboxylic and multifunctional acids: measurements and UNIFAC predictions.

    PubMed

    Peng, C; Chan, M N; Chan, C K

    2001-11-15

    The role of water-soluble organic compounds on the hygroscopic properties of atmospheric aerosols has recently been the subject of many studies. In particular, low molecular weight dicarboxylic acids and some multifunctional organic acids have been found or are expected to exist in atmospheric aerosols in urban, semiurban, rural, and remote sites. Unlike for their inorganic counterparts, the hygroscopic properties of organic acids have not been well characterized. In this study, the hygroscopic properties of selected water-soluble dicarboxylic acids (oxalic acid, malonic acid, succinic acid, and glutaric acid) and multifunctional acids (citric acid, DL-malic acid, and L-(+)-tartaric acid) were studied using single droplets levitated in an electrodynamic balance at 25 degrees C. The water activities of bulk samples of dilute solutions were also measured. Solute evaporation was observed in the dicarboxylic acids but not in the multifunctional acids. Oxalic acid, succinic acid, and glutaric acid droplets crystallize upon evaporation of water, but, except for glutaric acid droplets, do not deliquesce even at 90% relative humidity (RH). Mass transfer limitation of the deliquescence process was observed in glutaric acid. Neither crystallization nor deliquescence was observed in malonic acid, citric acid, DL-malic acid, or L-(+)-tartaric acid. Malonic acid and these three hydroxy-carboxylic acids absorb water even at RH much lower than their respective deliquescence RH. The growth factor (Gf), defined as the ratio of the particle diameter at RH = 10% to that at RH = 90%, of oxalic acid and succinic acid was close to unity, indicating no hygroscopicity in this range. The remaining acids (malonic acid, glutaric acid, citric acid, malic acid, and tartaric acid) showed roughly similar hygroscopicity of a Gf of 1.30-1.53, which is similar to that of "more hygroscopic" aerosols in field measurements reported in the literature. A generalized equation for these four acids, Gf

  2. Photolytic destruction of oxalate in aqueous mixed waste

    SciTech Connect

    Wang, F.T.; Lum, B.Y.

    1995-03-01

    In aqueous plutonium processing, residual oxalic acid can be destroyed (oxalate kill) by UV light with hydrogen peroxide (H{sub 2}O{sub 2}) in 1 M HCl solutions. By controlling the amount of H{sub 2}O{sub 2}, the oxalate kill process will not affect the chloride concentration. In nitric acid solutions, UV light alone can destroy the oxalic acid. However, with H{sub 2}O{sub 2}, the rate of destruction is faster. After the destruction of oxalic acid, the acidic solutions may be reusable without further purification process.

  3. Bi-anchoring organic sensitizers of type D-(π-A)2 comprising thiophene-2-acetonitrile as π-spacer and malonic acid as electron acceptor for dye sensitized solar cell applications

    NASA Astrophysics Data System (ADS)

    Reddy, Gachumale Saritha; Ramkumar, Sekar; Asiri, Abdullah M.; Anandan, Sambandam

    2015-06-01

    Two new bi-anchoring organic sensitizers of type D-(π-A)2 comprising the identical π-spacer (thiophene-2-acetonitrile) and electron acceptor (malonic acid) but different aryl amine as electron donors (diphenylamine and carbazole) were synthesized, characterized and fabricated metal free dye-sensitized solar cell devices. The intra molecular charge transfer property and electrochemical property of these dyes were investigated by molecular absorption, emission, cyclic voltammetric experiments and in addition, quantum chemical calculation studies were performed to provide sufficient driving force for the electron injection into the conduction band of TiO2 which leads to efficient charge collection. Among the fabricated devices, carbazole based device exhibits high current conversion efficiency (η = 4.7%) with a short circuit current density (JSC) 15.3 mA/cm2, an open circuit photo voltage (VOC) of 0.59 V and a fill factor of 0.44 under AM 1.5 illumination (85 mW/cm2) compared to diphenylamine based device.

  4. Complex dynamic behavior in the bromate-oxalic acid-acetone-Mn(II) oscillating reaction in a continuous stirred tank reactor (CSTR)

    NASA Astrophysics Data System (ADS)

    Silva, Lucyane C.; Faria, Roberto B.

    2007-05-01

    The oscillating reaction bromate-oxalic acid-acetone-Mn(II)-sulfuric acid was observed for the first time in a CSTR at 20 °C. Depending on the bromate concentrations and flow rate, the system showed large amplitude oscillations, two kinds of mixed mode oscillations, quasiperiodicity and bursts of large amplitude oscillations, all mapped in a phase diagram. More complex behavior was favored at low bromate concentrations. The system without acetone was discovered to oscillate too, but the more complex patterns were not seen, indicating that acetone is implied in their formation.

  5. Changes on organic acid secretion and accumulation in Plantago almogravensis Franco and Plantago algarbiensis Samp. under aluminum stress.

    PubMed

    Martins, Neusa; Gonçalves, Sandra; Andrade, Paula B; Valentão, Patrícia; Romano, Anabela

    2013-01-01

    We investigated the effect of Al (400μM) on organic acids secretion, accumulation and metabolism in Plantago almogravensis Franco and Plantago algarbiensis Samp. Al induced a significant reduction on root elongation only in P. algarbiensis. Both species accumulated considerable amounts of Al (>120μgg(-1)) in their tissues, roots exhibiting the highest contents (>900μgg(-1)). Al stimulated malonic acid secretion in P. algarbiensis, while citric, succinic and malic acids were secreted by P. almogravensis. Moreover, Al uptake was accompanied by substantial increases of citric, oxalic, malonic and fumaric acids contents in the plantlets of either species. Overall, the acid metabolizing enzymes were not directly involved in the Al induced organic acid secretion and accumulation. Our data suggest that Al detoxification in P. almogravensis implies both secretion of organic acids from roots and tolerance to high Al tissue concentrations, while in P. algarbiensis only the tolerance mechanism seems to be involved. PMID:23199681

  6. Changes on organic acid secretion and accumulation in Plantago almogravensis Franco and Plantago algarbiensis Samp. under aluminum stress.

    PubMed

    Martins, Neusa; Gonçalves, Sandra; Andrade, Paula B; Valentão, Patrícia; Romano, Anabela

    2013-01-01

    We investigated the effect of Al (400μM) on organic acids secretion, accumulation and metabolism in Plantago almogravensis Franco and Plantago algarbiensis Samp. Al induced a significant reduction on root elongation only in P. algarbiensis. Both species accumulated considerable amounts of Al (>120μgg(-1)) in their tissues, roots exhibiting the highest contents (>900μgg(-1)). Al stimulated malonic acid secretion in P. algarbiensis, while citric, succinic and malic acids were secreted by P. almogravensis. Moreover, Al uptake was accompanied by substantial increases of citric, oxalic, malonic and fumaric acids contents in the plantlets of either species. Overall, the acid metabolizing enzymes were not directly involved in the Al induced organic acid secretion and accumulation. Our data suggest that Al detoxification in P. almogravensis implies both secretion of organic acids from roots and tolerance to high Al tissue concentrations, while in P. algarbiensis only the tolerance mechanism seems to be involved.

  7. Combined administration of oxalic acid, succimer and its analogue for the reversal of gallium arsenide-induced oxidative stress in rats.

    PubMed

    Flora, Swaran J S; Kannan, Gurusamy M; Pant, Bhagwat P; Jaiswal, Devendra K

    2002-06-01

    Gallium arsenide (GaAs), a group III-VA intermetallic semiconductor, possesses superior electronic and optical properties and has a wide application in the electronics industry. Exposure to GaAs in the semiconductor industry is a potential occupational hazard because cleaning and slicing GaAs ingots to yield the desired wafer could generate GaAs particles. The ability of GaAs to induce oxidative stress has not yet been reported. The present study reports the role of oxidative stress in GaAs-induced haematological and liver disorders and its possible reversal overturn by administration of meso-2,3-dimercaptosuccinic acid (DMSA) and one of its analogue, monoisoamyl DMSA (MiADMSA), either individually or in combination with oxalic acid. While DMSA and MiADMSA are potential arsenic chelators, oxalic acid is reported to be an effective gallium chelator. Male rats were exposed to 10 mg/kg GaAs orally, 5 days a week for 8 weeks. GaAs exposure was then stopped and rats were given a 0.5 mmol/kg dose of succimers (DMSA or MiADMSA), oxalic acid or a combination of the two, intraperitoneally once daily for 5 consecutive days. We found a significant fall in blood delta-aminolevulinic acid dehydratase (ALAD) activity and blood glutathione (GSH) level, and an increased urinary excretion of delta-aminolevulinic acid (ALA) and an increased malondialdehyde (MDA) level in erythrocytes of rats exposed to GaAs. Hepatic GSH levels decreased, whereas there was an increase in GSSG and MDA levels. The results suggest a role of oxidative stress in GaAs-induced haematological and hepatic damage. Administration of DMSA and MiADMSA produced effective recovery in most of the above variables. However, a greater effectiveness of the chelation treatment (i.e. removal of both gallium and arsenic from body organs) could be achieved by combined administration of succimer (DMSA) with oxalic acid since, after MiADMSA administration, a marked loss of essential metals (copper and zinc) is of concern.

  8. Zirconium-carbon hybrid sorbent for removal of fluoride from water: oxalic acid mediated Zr(IV) assembly and adsorption mechanism

    PubMed Central

    Halla, Velazquez-Jimenez Litza; Hurt Robert, H; Juan, Matos; Rene, Rangel-Mendez Jose

    2014-01-01

    When activated carbon (AC) is modified with zirconium(IV) by impregnation or precipitation, the fluoride adsorption capacity is typically improved. There is significant potential to improve these hybrid sorbent by controlling the impregnation conditions, which determine the assembly and dispersion of the Zr phases on carbon surfaces. Here, commercial activated carbon was modified with Zr(IV) together with oxalic acid (OA) used to maximize the zirconium dispersion and enhance fluoride adsorption. Adsorption experiments were carried out at pH 7 and 25 °C with a fluoride concentration of 40 mg L−1. The OA/Zr ratio was varied to determine the optimal conditions for subsequent fluoride adsorption. The data was analyzed using the Langmuir and Freundlich isotherm models. FTIR, XPS and the surface charge distribution were performed to elucidate the adsorption mechanism. Potentiometric titrations showed that the modified activated carbon (ZrOx-AC) possesses positive charge at pH lower than 7, and FTIR analysis demonstrated that zirconium ions interact mainly with carboxylic groups on the activated carbon surfaces. Moreover, XPS analysis demonstrated that Zr(IV) interacts with oxalate ions, and the fluoride adsorption mechanism is likely to involve –OH− exchange from zirconyl oxalate complexes. PMID:24359079

  9. Zirconium-carbon hybrid sorbent for removal of fluoride from water: oxalic acid mediated Zr(IV) assembly and adsorption mechanism.

    PubMed

    Velazquez-Jimenez, Litza Halla; Hurt, Robert H; Matos, Juan; Rangel-Mendez, Jose Rene

    2014-01-21

    When activated carbon (AC) is modified with zirconium(IV) by impregnation or precipitation, the fluoride adsorption capacity is typically improved. There is significant potential to improve these hybrid sorbents by controlling the impregnation conditions, which determine the assembly and dispersion of the Zr phases on carbon surfaces. Here, commercial activated carbon was modified with Zr(IV) together with oxalic acid (OA) used to maximize the zirconium dispersion and enhance fluoride adsorption. Adsorption experiments were carried out at pH 7 and 25 °C with a fluoride concentration of 40 mg L(-1). The OA/Zr ratio was varied to determine the optimal conditions for subsequent fluoride adsorption. The data was analyzed using the Langmuir and Freundlich isotherm models. FTIR, XPS, and the surface charge distribution were performed to elucidate the adsorption mechanism. Potentiometric titrations showed that the modified activated carbon (ZrOx-AC) possesses positive charge at pH lower than 7, and FTIR analysis demonstrated that zirconium ions interact mainly with carboxylic groups on the activated carbon surfaces. Moreover, XPS analysis demonstrated that Zr(IV) interacts with oxalate ions, and the fluoride adsorption mechanism is likely to involve -OH(-) exchange from zirconyl oxalate complexes.

  10. Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

    USGS Publications Warehouse

    Morgan, G.B.; Chou, I.-Ming; Pasteris, J.D.

    1992-01-01

    Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H2C2O4 ?? 2H2O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230-750??C, with bulk fluid densities in the range 0.01-0.53 g/cm3. Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230-350??C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO2 + CO + 3H2O. A process of the form CO + H2O = CO2 + H2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H2O-CO2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of Saxena and Fei (1988). Such disagreement suggests that the formations of CH4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600-650??C. These results have applications to fluid processes in geological

  11. An improved thermodynamic model for the complexation of trivalent actinides and lanthanide with oxalic acid valid to high ionic strength.

    SciTech Connect

    Xiong, Yongliang; Thakur, Punam; Borkowski, Marian

    2015-07-30

    The dissociation constants of oxalic acid (Ox), and the stability constants of Am3+, Cm3+ and Eu3+ with Ox2– have been determined at 25 °C, over a range of concentration varying from 0.1 to 6.60 m NaClO4 using potentiometric titration and extraction techniques, respectively. The experimental data support the formation of complexes, M(Ox)n3 – 2n, where (M = Am3+, Cm3+ and Eu3+ and n = 1 and 2). The dissociation constant and the stability constant values measured as a function of NaClO4 concentration were used to estimate the Pitzer parameters for the respective interactions of Am3+, Cm3+ and Eu3+ with Ox. Furthermore, the stability constants data of Am3+ –Ox measured in NaClO4 and in NaCl solutions from the literature were simultaneously fitted in order to refine the existing actinide–oxalate complexation model that can be used universally in the safety assessment of radioactive waste disposal. The thermodynamic stability constant: log β0101 = 6.30 ± 0.06 and log β0102 = 10.84 ± 0.06 for Am3+ was obtained by simultaneously fitting data in NaCl and NaClO4 media. Additionally, log β0101 = 6.72 ± 0.08 and log β0102 = 11.05 ± 0.09 for the Cm3+ and log β0101 = 6.67 ± 0.08 and log β0102 = 11.15 ± 0.09 for the Eu3+ were calculated by extrapolation of data to zero ionic strength in NaClO4 medium only. For all stability constants, the Pitzer model gives an excellent representation of the data using interaction parameters β(0), β(1), and CΦ determined in this work. The thermodynamic model developed in this work will be useful in accurately modeling the potential solubility of trivalent

  12. 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.

  13. 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. PMID:27179243

  14. 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.

  15. High abundances of oxalic, azelaic, and glyoxylic acids and methylglyoxal in the open ocean with high biological activity: Implication for secondary OA formation from isoprene

    NASA Astrophysics Data System (ADS)

    Bikkina, Srinivas; Kawamura, Kimitaka; Miyazaki, Yuzo; Fu, Pingqing

    2014-05-01

    Atmospheric dicarboxylic acids (DCA) are a ubiquitous water-soluble component of secondary organic aerosols (SOA), which can act as cloud condensation nuclei (CCN), affecting the Earth's climate. Despite the high abundances of oxalic acid and related compounds in the marine aerosols, there is no consensus on what controls their distributions over the open ocean. Marine biological productivity could play a role in the production of DCA, but there is no substantial evidence to support this hypothesis. Here we present latitudinal distributions of DCA, oxoacids and α-dicarbonyls in the marine aerosols from the remote Pacific. Their concentrations were found several times higher in more biologically influenced aerosols (MBA) than less biologically influenced aerosols. We propose isoprene and unsaturated fatty acids as sources of DCA as inferred from significantly higher abundances of isoprene-SOA tracers and azelaic acid in MBA. These results have implications toward the reassessment of climate forcing feedbacks of marine-derived SOA.

  16. A simple, efficient and environmentally benign synthetic protocol for the synthesis of spirooxindoles using choline chloride-oxalic acid eutectic mixture as catalyst/solvent system.

    PubMed

    Khandelwal, Sarita; Rajawat, Anshu; Tailor, Yogesh Kumar; Kumar, Mahendra

    2014-01-01

    An efficient and environmentally benign domino protocol has been presented for the synthesis of structurally diverse spirooxindoles spiroannulated with pyranopyridopyrimidines, indenopyridopyrimidines, and chromenopyridopyrimidines involving three-component reaction of aminouracils, isatins and cyclic carbonyl compounds in deep eutectic solvent (choline chloride-oxalic acid: 1:1) which acts as efficient catalyst and environmentally benign reaction medium. The present protocol offers several advantages such as operational simplicity with easy workup, shorter reaction times excellent yields with superior atom economy and environmentally benign reaction conditions with the use of cost-effective, recyclable, non-toxic and bio-degradable DES as catalyst/solvent.

  17. A simple, efficient and environmentally benign synthetic protocol for the synthesis of spirooxindoles using choline chloride-oxalic acid eutectic mixture as catalyst/solvent system.

    PubMed

    Khandelwal, Sarita; Rajawat, Anshu; Tailor, Yogesh Kumar; Kumar, Mahendra

    2014-01-01

    An efficient and environmentally benign domino protocol has been presented for the synthesis of structurally diverse spirooxindoles spiroannulated with pyranopyridopyrimidines, indenopyridopyrimidines, and chromenopyridopyrimidines involving three-component reaction of aminouracils, isatins and cyclic carbonyl compounds in deep eutectic solvent (choline chloride-oxalic acid: 1:1) which acts as efficient catalyst and environmentally benign reaction medium. The present protocol offers several advantages such as operational simplicity with easy workup, shorter reaction times excellent yields with superior atom economy and environmentally benign reaction conditions with the use of cost-effective, recyclable, non-toxic and bio-degradable DES as catalyst/solvent. PMID:25329839

  18. Directed synthesis of crystalline plutonium (III) and (IV) oxalates: accessing redox-controlled separations in acidic solutions

    SciTech Connect

    Runde, Wolfgang; Brodnax, Lia F; Goff, George S; Bean, Amanda C; Scott, Brian L

    2009-01-01

    Both binary and ternary solid complexes of Pu(III) and Pu(IV) oxalates have been previously reported in the literature. However, uncertainties regarding the coordination chemistry and the extent of hydration of some compounds remain mainly because of the absence of any crystallographic characterization. Single crystals of hydrated oxalates of Pu(III), Pu{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 6}{center_dot}3H{sub 2}O (I) and Pu(IV), KPu(C{sub 2}O{sub 4}){sub 2}(OH){center_dot}2.5H{sub 2}O (II), were synthesized under moderate hydrothermal conditions and characterized by single crystal X-ray diffraction studies. Compounds I and II are the first plutonium(III) or (IV) oxalate compounds to be structurally characterized via single crystal X-ray diffraction studies. Crystallographic data for I: monoclinic, space group P21/c, a = 11.246(3) A, b = 9.610(3) A, c = 10.315(3) A, Z = 4 and II: monoclinic, space group C2/c, a = 23.234(14) A, b = 7.502(4) A, c = 13.029(7) A, Z = 8.

  19. Dentin Hypersensitivity and Oxalates

    PubMed Central

    Cunha-Cruz, J.; Stout, J.R.; Heaton, L.J.; Wataha, J.C.

    2011-01-01

    Treatment of dentin hypersensitivity with oxalates is common, but oxalate efficacy remains unclear. Our objective was to systematically review clinical trials reporting an oxalate treatment compared with no treatment or placebo with a dentin hypersensitivity outcome. Risk-of-bias assessment and data extraction were performed independently by two reviewers. Standardized mean differences (SMD) were estimated by random-effects meta-analysis. Of 677 unique citations, 12 studies with high risk-of-bias were included. The summary SMD for 3% monohydrogen-monopotassium oxalate (n = 8 studies) was -0.71 [95% Confidence Interval: -1.48, 0.06]. Other treatments, including 30% dipotassium oxalate (n = 1), 30% dipotassium oxalate plus 3% monohydrogen monopotassium oxalate (n = 3), 6% monohydrogen monopotassium oxalate (n = 1), 6.8% ferric oxalate (n = 1), and oxalate-containing resin (n = 1), also were not statistically significantly different from placebo treatments. With the possible exception of 3% monohydrogen monopotassium oxalate, available evidence currently does not support the recommendation of dentin hypersensitivity treatment with oxalates. PMID:21191127

  20. α- And β Pahases of oxalic acid, H 2C 2O 4: Vibrational spectra, normal-coordinate calculations, and intermolecular forces

    NASA Astrophysics Data System (ADS)

    De Villepin, J.; Novak, A.; Bougeard, D.

    1982-12-01

    Infrared (4000-30 cm -1) and Raman (4000-0 cm -) spectra of single crystals of α-oxalic acid (Pcab, Z=4) have been investigated at 100 and 300 K. A complete assignment of all modes in terms of symmetry species and to internal, librational, translational, and hydrogen bond motions is given. In order to interpret the spectra and to determine the crystal field, several normal-coordinate calculations (free molecule, rigid body model, unit cell as a supermolecule) have been carried out. The calculations are in good agreement with the experimental results and show the importance of different intermolecular forces: OH … O hydrogen bonds and very short C … O interactions lead to both unusually strong correlation field splitting and high lattice frequencies while quadrupole-quadrupole and CO dipole-dipole interactions influence lattice and some internal vibrations, respectively. The intermolecular potentials obtained for α-oxalic acid are transferable to the β form having a different crystal structure (P2 1/c, Z = 2) and stronger hydrogen bonds.

  1. Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 1. Minor structures

    USGS Publications Warehouse

    Leenheer, J.A.; Wershaw, R. L.; Reddy, M.M.

    1995-01-01

    An investigation of the strong-acid characteristics (pKa 3.0 or less) of fulvic acid from the Suwannee River, Georgia, was conducted. Quantitative determinations were made for amino acid and sulfur-containing acid structures, oxalate half-ester structures, malonic acid structures, keto acid structures, and aromatic carboxyl-group structures. These determinations were made by using a variety of spectrometric (13C-nuclear magnetic resonance, infrared, and ultraviolet spectrometry) and titrimetric characterizations on fulvic acid or fulvic acid samples that were chemically derivatized to indicate certain functional groups. Only keto acid and aromatic carboxyl-group structures contributed significantly to the strong-acid characteristics of the fulvic acid; these structures accounted for 43% of the strong-acid acidity. The remaining 57% of the strong acids are aliphatic carboxyl groups in unusual and/or complex configurations for which limited model compound data are available.

  2. OXALATE MASS BALANCE DURING CHEMICAL CLEANING IN TANK 6F

    SciTech Connect

    Poirier, M.; Fink, S.

    2011-07-22

    The Savannah River Remediation (SRR) is preparing Tank 6F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning to determine whether the tank is ready for closure. SRR personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of the chemical cleaning process. Analysis of the anions showed the measured oxalate removed from Tank 6F to be approximately 50% of the amount added in the oxalic acid. To close the oxalate mass balance, the author collected solid samples, leached them with nitric acid, and measured the concentration of cations and anions in the leachate. Some conclusions from this work are: (1) Approximately 65% of the oxalate added as oxalic acid was removed with the decanted liquid. (2) Approximately 1% of the oxalate (added to the tank as oxalic acid) formed precipitates with compounds such as nickel, manganese, sodium, and iron (II), and was dissolved with nitric acid. (3) As much as 30% of the oxalate may have decomposed forming carbon dioxide. The balance does not fully account for all the oxalate added. The offset represents the combined uncertainty in the analyses and sampling.

  3. 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

  4. Kinetics of Mo, Ni, V and Al leaching from a spent hydrodesulphurization catalyst in a solution containing oxalic acid and hydrogen peroxide.

    PubMed

    Szymczycha-Madeja, Anna

    2011-02-28

    The kinetics of molybdenum, nickel, vanadium and aluminium leaching from a spent hydrodesulphurization catalyst in a solution containing oxalic acid and hydrogen peroxide was investigated. The effects of temperature and particle size were examined. In addition, the reaction mechanism for the dissolution of the spent catalyst was discussed. The results of the kinetic analysis for various experimental conditions indicated that the reaction rate of leaching process is controlled by chemical reaction at the particle surface. The values of the activation energies of 31±2, 36±4, 30±4 and 57±3 kJ mol(-1) for Mo, Ni, V and Al, respectively, are characteristic for mechanism controlled by chemical reaction. PMID:21167639

  5. Formyl-coenzyme A (CoA):oxalate CoA-transferase from the acidophile Acetobacter aceti has a distinctive electrostatic surface and inherent acid stability

    PubMed Central

    Mullins, Elwood A; Starks, Courtney M; Francois, Julie A; Sael, Lee; Kihara, Daisuke; Kappock, T Joseph

    2012-01-01

    Bacterial formyl-CoA:oxalate CoA-transferase (FCOCT) and oxalyl-CoA decarboxylase work in tandem to perform a proton-consuming decarboxylation that has been suggested to have a role in generalized acid resistance. FCOCT is the product of uctB in the acidophilic acetic acid bacterium Acetobacter aceti. As expected for an acid-resistance factor, UctB remains folded at the low pH values encountered in the A. aceti cytoplasm. A comparison of crystal structures of FCOCTs and related proteins revealed few features in UctB that would distinguish it from nonacidophilic proteins and thereby account for its acid stability properties, other than a strikingly featureless electrostatic surface. The apparently neutral surface is a result of a “speckled” charge decoration, in which charged surface residues are surrounded by compensating charges but do not form salt bridges. A quantitative comparison among orthologs identified a pattern of residue substitution in UctB that may be a consequence of selection for protein stability by constant exposure to acetic acid. We suggest that this surface charge pattern, which is a distinctive feature of A. aceti proteins, creates a stabilizing electrostatic network without stiffening the protein or compromising protein–solvent interactions. PMID:22374910

  6. Formyl-coenzyme A (CoA):oxalate CoA-transferase from the acidophile Acetobacter aceti has a distinctive electrostatic surface and inherent acid stability.

    PubMed

    Mullins, Elwood A; Starks, Courtney M; Francois, Julie A; Sael, Lee; Kihara, Daisuke; Kappock, T Joseph

    2012-05-01

    Bacterial formyl-CoA:oxalate CoA-transferase (FCOCT) and oxalyl-CoA decarboxylase work in tandem to perform a proton-consuming decarboxylation that has been suggested to have a role in generalized acid resistance. FCOCT is the product of uctB in the acidophilic acetic acid bacterium Acetobacter aceti. As expected for an acid-resistance factor, UctB remains folded at the low pH values encountered in the A. aceti cytoplasm. A comparison of crystal structures of FCOCTs and related proteins revealed few features in UctB that would distinguish it from nonacidophilic proteins and thereby account for its acid stability properties, other than a strikingly featureless electrostatic surface. The apparently neutral surface is a result of a "speckled" charge decoration, in which charged surface residues are surrounded by compensating charges but do not form salt bridges. A quantitative comparison among orthologs identified a pattern of residue substitution in UctB that may be a consequence of selection for protein stability by constant exposure to acetic acid. We suggest that this surface charge pattern, which is a distinctive feature of A. aceti proteins, creates a stabilizing electrostatic network without stiffening the protein or compromising protein-solvent interactions.

  7. Oxalic acid mediated synthesis of WO{sub 3}.H{sub 2}O nanoplates and self-assembled nanoflowers under mild conditions

    SciTech Connect

    Li Linzhi; Zhao Jingzhe; Wang Yi; Li Yunling; Ma Dechong; Zhao Yan; Hou Shengnan; Hao Xinli

    2011-07-15

    Tungsten oxide hydrate (WO{sub 3}.H{sub 2}O) nanoplates and flower-like assemblies were successfully synthesized via a simple aqueous method. The effects of reaction parameters in solution on the preparation were studied. Nanoplates and nanoflowers can be selectively prepared by changing the amount of H{sub 2}C{sub 2}O{sub 4}. In-situ assembly of nanoplates to nanoflowers was also proposed for the formation of assembled nanostructures. In addition, the reaction time and temperature have important effects on the sizes of the as-obtained samples. Crystal structure, morphology, and composition of final nanostructures were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Optical properties of the synthesized samples and the growth mechanism were studied by UV-vis detection. Degradation experiments of Rhodamine B (RhB) were also performed on samples of nanoplates and nanoflowers under visible light illumination. Nanoflower sample exhibited preferable photocatalytic property to nanoplate sample. - Graphical abstract: The oxalic acid has a key role for the structure of WO{sub 3}.H{sub 2}O evolution from plates to flowers and the dehydration process of WO{sub 3}.2H{sub 2}O to WO{sub 3}.H{sub 2}O. Highlights: > Tungsten oxides hydrate was synthesized via a simple aqueous method. > The size of WO{sub 3}.H{sub 2}O was controlled by the reaction time and temperature. > The assembly of WO{sub 3}.H{sub 2}O nanoplates to nanoflowers was achieved with higher H{sub 2}C{sub 2}O{sub 4}/Na{sub 2}WO{sub 4} ratio. > Oxalic acid has a key role in the dehydration process of WO{sub 3}.2H{sub 2}O to WO{sub 3}.H{sub 2}O.

  8. Commentary on Malone: Who Founded Behaviorism?

    PubMed

    Reese, Hayne W

    2015-05-01

    Malone (The Behavior Analyst, 37, 1-12 2014) argued that the emergence of behaviorism was inevitable with or without Watson's participation, mainly because protobehavioral ideas and dissatisfaction with classical structuralism were already widespread. However, the first premise is questionable because many of the ideas Malone cited were consistent with structuralism rather than behaviorism, and even if both premises were true they would not make the emergence of behaviorism-or anything else-inevitable. Historical evidence for inevitability is always retrospective and therefore always allows the logical fallacy of "after this, therefore because of this." In the relevant real world Watson existed, he was a psychologist, he was the first to publish an article that described a "behaviorism," and he promoted his behaviorism in later works. Stories about what would have happened without Watson's participation are therefore counterfactual and this lack of historicity makes the stories fictional rather than scientific. In the real world, Watson founded behaviorism. PMID:27606163

  9. Oxalates in some Indian green leafy vegetables.

    PubMed

    Radek, M; Savage, G P

    2008-05-01

    The soluble and total oxalate contents of 11 leafy vegetables grown in India were determined. Spinach, purple and green amaranth and colocasia contained high levels of total oxalates, which ranged from 5,138.0 +/- 37.6 mg/100 g dry matter up to 12,576.1 +/- 107.9 mg/100 g dry matter. Seven other leafy vegetables (curry, drumstick, shepu, fenugreek, coriander, radish and onion stalks) contained only insoluble oxalate, which ranged from 209.0 +/- 5.0 mg/100 g dry matter to 2,774.9 +/-18.4 mg/100 g dry matter. In vitro digestion of the samples showed that the gastric available oxalate was 10% lower than the values obtained from acid extraction and that intestinal available oxalate was 20% lower than the values obtained following hot water extraction. The percentage calcium bound in the insoluble oxalate fraction of the dried leafy vegetables ranged from 3.3% to 86.7% of the total calcium. Addition of four different sources of calcium (low fat milk, whole milk, calcium carbonate and calcium sulphate) resulted in a range of 32-100% reductions of intestinal available oxalate in the mixture. PMID:18335334

  10. Evidence for size and charge permselectivity of rat ascending colon. Effects of ricinoleate and bile salts on oxalic acid and neutral sugar transport.

    PubMed Central

    Kathpalia, S C; Favus, M J; Coe, F L

    1984-01-01

    We have measured unidirectional transmural fluxes of oxalate and neutral sugars across rat ascending colon in vitro, under short-circuit conditions, to characterize permeability barriers selective for size and charge. Ionic oxalate appears to be transported preferentially to sodium oxalate. Mucosal addition of taurocholate (1 mM), deoxycholate (1 mM), or ricinoleate (1 mM) increased bidirectional oxalate fluxes, and the ricinoleate effects were independent of medium calcium. Bidirectional fluxes of uncharged sugar molecules fell sharply at molecular weights above 76 (molecular radius above 3 A), and oxalate transport was retarded relative to that of uncharged molecules of similar size, suggesting that there is both size and charge permselectivity. Ricinoleate increased fluxes of all neutral molecules tested but changed neither the exclusion limits nor the cation selectivity of the epithelium. Bile salts and ricinoleate increase oxalate transport, probably by making more channels available, but do not alter size and charge selectivity. PMID:6432849

  11. Size distributions of nano/micron dicarboxylic acids and inorganic ions in suburban PM episode and non-episodic aerosol

    NASA Astrophysics Data System (ADS)

    Hsieh, Li-Ying; Kuo, Su-Ching; Chen, Chien-Lung; Tsai, Ying I.

    The distribution of nano/micron dicarboxylic acids and inorganic ions in size-segregated suburban aerosol of southern Taiwan was studied for a PM episode and a non-episodic pollution period, revealing for the first time the distribution of these nanoscale particles in suburban aerosols. Inorganic species, especially nitrate, were present in higher concentrations during the PM episode. A combination of gas-to-nuclei conversion of nitrate particles and accumulation of secondary photochemical products originating from traffic-related emissions was likely a crucial cause of the PM episode. Sulfate, ammonium, and oxalic acid were the dominant anion, cation, and dicarboxylic acid, respectively, accounting for a minimum of 49% of the total anion, cation or dicarboxylic acid mass. Peak concentrations of these species occurred at 0.54 μm in the droplet mode during both non-episodic and PM episode periods, indicating an association with cloud-processed particles. On average, sulfate concentration was 16-17 times that of oxalic acid. Oxalic acid was nevertheless the most abundant dicarboxylic acid during both periods, followed by succinic, malonic, maleic, malic and tartaric acid. The mass median aerodynamic diameter (MMAD) of oxalic acid was 0.77 μm with a bi-modal presence at 0.54 μm and 18 nm during non-episodic pollution and an MMAD of 0.67 μm with mono-modal presence at 0.54 μm in PM episode aerosol. The concomitant formation of malonic acid and oxalic acid was attributed to in-cloud processes. During the PM episode in the 5-100 nm nanoscale range, an oxalic acid/sulfate mass ratio of 40.2-82.3% suggested a stronger formation potential for oxalic acid than for sulfate in the nuclei mode. For total cations (TC), total inorganic anions (TIA) and total dicarboxylic acids (TDA), major contributing particles were in the droplet mode, with least in the nuclei mode. The ratio of TDA to TIA in the nuclei mode increased greatly from 8.40% during the non-episodic pollution

  12. Organic acids in continental background aerosols

    NASA Astrophysics Data System (ADS)

    Limbeck, Andreas; Puxbaum, Hans

    With a newly developed method aerosol samples from three distinctly different continental sites were analyzed: an urban site (Vienna), a savanna site in South Africa (Nylsvley Nature Reserve, NNR) and a free tropospheric continental background site (Sonnblick Observatory, SBO). In all samples a range of monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) has been identified and quantified. The three most abundant MCAs in Vienna were the C18, C16 and C14 acids with concentrations of 66, 45 and 36 ng m -3, respectively. At the mid tropospheric background site (SBO) the three most abundant MCAs were the C18, C16 and C12 acid. For the DCAs at all three sites oxalic, malonic and succinic acid were the dominant compounds. For some individual compounds an information about the sources could be obtained. For example the determined unsaturated MCAs in South Africa appear to result from biogenic sources whereas in Vienna those acids are considered to be derived from combustion processes. Oxalic and glyoxalic acid appear to have a free tropospheric air chemical source. The relative high amounts at SBO in comparison to Vienna can only be explained by secondary formation of oxalic acid in the atmosphere.

  13. Contribution of dietary oxalate to urinary oxalate excretion

    NASA Technical Reports Server (NTRS)

    Holmes, R. P.; Goodman, H. O.; Assimos, D. G.

    2001-01-01

    BACKGROUND: The amount of oxalate excreted in urine has a significant impact on calcium oxalate supersaturation and stone formation. Dietary oxalate is believed to make only a minor (10 to 20%) contribution to the amount of oxalate excreted in urine, but the validity of the experimental observations that support this conclusion can be questioned. An understanding of the actual contribution of dietary oxalate to urinary oxalate excretion is important, as it is potentially modifiable. METHODS: We varied the amount of dietary oxalate consumed by a group of adult individuals using formula diets and controlled, solid-food diets with a known oxalate content, determined by a recently developed analytical procedure. Controlled solid-food diets were consumed containing 10, 50, and 250 mg of oxalate/2500 kcal, as well as formula diets containing 0 and 180 mg oxalate/2500 kcal. Changes in the content of oxalate and other ions were assessed in 24-hour urine collections. RESULTS: Urinary oxalate excretion increased as dietary oxalate intake increased. With oxalate-containing diets, the mean contribution of dietary oxalate to urinary oxalate excretion ranged from 24.4 +/- 15.5% on the 10 mg/2500 kcal/day diet to 41.5 +/- 9.1% on the 250 mg/2500 kcal/day diet, much higher than previously estimated. When the calcium content of a diet containing 250 mg of oxalate was reduced from 1002 mg to 391 mg, urinary oxalate excretion increased by a mean of 28.2 +/- 4.8%, and the mean dietary contribution increased to 52.6 +/- 8.6%. CONCLUSIONS: These results suggest that dietary oxalate makes a much greater contribution to urinary oxalate excretion than previously recognized, that dietary calcium influences the bioavailability of ingested oxalate, and that the absorption of dietary oxalate may be an important factor in calcium oxalate stone formation.

  14. A review of oxalate poisoning in domestic animals: tolerance and performance aspects.

    PubMed

    Rahman, M M; Abdullah, R B; Wan Khadijah, W E

    2013-08-01

    Published data on oxalate poisoning in domestic animals are reviewed, with a focus on tolerance and performance. Oxalic acid is one of a number of anti-nutrients found in forage. It can bind with dietary calcium (Ca) or magnesium (Mg) to form insoluble Ca or Mg oxalate, which then may lead to low serum Ca or Mg levels as well as to renal failure because of precipitation of these salts in the kidneys. Dietary oxalate plays an important role in the formation of Ca oxalate, and a high dietary intake of Ca may decrease oxalate absorption and its subsequent urinary excretion. Oxalate-rich plants can be supplemented with other plants as forage for domestic animals, which may help to reduce the overall intake of oxalate-rich plants. Non-ruminants appear to be more sensitive to oxalate than ruminants because in the latter, rumen bacteria help to degrade oxalate. If ruminants are slowly exposed to a diet high in oxalate, the population of oxalate-degrading bacteria in the rumen increases sufficiently to prevent oxalate poisoning. However, if large quantities of oxalate-rich plants are eaten, the rumen is overwhelmed and unable to metabolize the oxalate and oxalate-poisoning results. Based on published data, we consider that <2.0% soluble oxalate would be an appropriate level to avoid oxalate poisoning in ruminants, although blood Ca level may decrease. In the case of non-ruminants, <0.5% soluble oxalate may be acceptable. However, these proposed safe levels of soluble oxalate should be regarded as preliminary. Further studies, especially long-term studies, are needed to validate and improve the recommended safe levels in animals. This review will encourage further research on the relationships between dietary oxalate, other dietary factors and renal failure in domestic animals.

  15. 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.

  16. Longitudinal distributions of dicarboxylic acids, ω-oxoacids, pyruvic acid, α-dicarbonyls, and fatty acids in the marine aerosols from the central Pacific including equatorial upwelling

    NASA Astrophysics Data System (ADS)

    Hoque, Mir Md. Mozammal; Kawamura, Kimitaka

    2016-03-01

    Remote marine aerosol samples (total suspended particles) were collected during a cruise in the central Pacific from Japan to Mexico (1°59'N-35°N and 171°54'E-90°58'W). The aerosol samples were analyzed for dicarboxylic acids (C2-C11), ω-oxoacids, pyruvic acid, α-dicarbonyls, and fatty acids as well as organic and elemental carbon, water-soluble organic carbon, and total nitrogen (WSTN). During the study, diacids were the most abundant compound class followed by fatty acids, ω-oxoacids, and α-dicarbonyls. Molecular compositions of diacids showed a predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids. Oxalic acid comprises 74% of total diacids. This result suggests that photochemical production of oxalic acid is significant over the central Pacific. Spatial distributions of diacids, ω-oxoacids, pyruvic acid, α-dicarbonyls, and fatty acids together with total carbon and WSTN showed higher abundances in the eastern equatorial Pacific where the upwelling of high-nutrient waters followed by high biological productivity is common, indicating that their in situ production is important in the warmer central Pacific through photochemical oxidation from their gaseous and particulate precursors. This study demonstrates that there is a strong linkage in biogeochemical cycles of carbon in the sea-air interface via ocean upwelling, phytoplankton productivity, sea-to-air emissions of organic matter, and formation of secondary organic aerosols in the eastern equatorial Pacific.

  17. Biogeochemistry of oxalate in the antarctic cryptoendolithic lichen-dominated community.

    PubMed

    Johnston, C G; Vestal, J R

    1993-05-01

    Cryptoendolithic (hidden in rock) lichen-dominated microbial communities from the Ross Desert of Antarctica were shown to produce oxalate (oxalic acid). Oxalate increased mineral dissolution, which provides nutrients, creates characteristic weathering patterns, and may ultimately influence the biological residence time of the community. Oxalate was the only organic acid detectable by HPLC, and its presence was verified by GC/MS. Community photosynthetic metabolism was involved in oxalate production since rates of (14)C-oxalate production from (14)C02 were higher in light than in dark incubations. Flaking of the sandstone at the level of the lichen-dominated zone a few millimeters beneath the rock surface can be explained by dissolution of the sandstone cement, which was enhanced by Si, Fe, and Al oxalate complex formation. Added oxalate was observed to increase the solubility of Si, Fe, Al, P, and K. Oxalate's ability to form soluble trivalent metal-oxalate complexes correlated with the observed order of metal oxide depletion from the lichen-dominated zone (Mn > Fe > Al). Thermodynamic calculations predict that Fe oxalate complex formation mobilizes amorphous Fe oxides (ferrihydrite) in the lichen-dominated zone, and where oxalate is depleted, ferrihydrite should precipitate. Hematite, a more crystalline Fe oxide, should remain solid at in situ oxalate concentrations. Oxalate was not a carbon source for the indigenous heterotrophs, but the microbiota were involved in oxalate mineralization to CO2, since oxalate mineralization was reduced in poisoned incubations. Photooxidation of oxalate to C02 coupled with photoreduction of Fe(Ill) may be responsible for oxalate removal in situ, since rates of (14)C-oxalate mineralization in dark incubations were at least 50% lower than those in the light. Removal of oxalate from Si, Fe, and Al complexes should allow free dissolved Si, Fe, and Al to precipitate as amorphous silicates and metal oxides. This may explain increased

  18. Oxalate-degrading microorganisms or oxalate-degrading enzymes: which is the future therapy for enzymatic dissolution of calcium-oxalate uroliths in recurrent stone disease?

    PubMed

    Peck, Ammon B; Canales, Benjamin K; Nguyen, Cuong Q

    2016-02-01

    Renal urolithiasis is a pathological condition common to a multitude of genetic, physiological and nutritional disorders, ranging from general hyperoxaluria to obesity. The concept of quickly dissolving renal uroliths via chemolysis, especially calcium-oxalate kidney stones, has long been a clinical goal, but yet to be achieved. Over the past 25 years, there has been a serious effort to examine the prospects of using plant and microbial oxalate-degrading enzymes known to catabolize oxalic acid and oxalate salts. While evidence is emerging that bacterial probiotics can reduce recurrent calcium-oxalate kidney stone disease by lowering systemic hyperoxaluria, the possible use of free oxalate-degrading enzyme therapy remains a challenge with several hurdles to overcome before reaching clinical practice. PMID:26645869

  19. Acute oxalate nephropathy caused by ethylene glycol poisoning

    PubMed Central

    Seo, Jung Woong; Lee, Jong-Ho; Son, In Sung; Kim, Yong Jin; Kim, Do Young; Hwang, Yong; Chung, Hyun Ah; Choi, Hong Seok; Lim, So Dug

    2012-01-01

    Ethylene glycol (EG) is a sweet-tasting, odorless organic solvent found in many agents, such as anti-freeze. EG is composed of four organic acids: glycoaldehyde, glycolic acid, glyoxylic acid and oxalic acid in vivo. These metabolites are cellular toxins that can cause cardio-pulmonary failure, life-threatening metabolic acidosis, central nervous system depression, and kidney injury. Oxalic acid is the end product of EG, which can precipitate to crystals of calcium oxalate monohydrate in the tubular lumen and has been linked to acute kidney injury. We report a case of EG-induced oxalate nephropathy, with the diagnosis confirmed by kidney biopsy, which showed acute tubular injury of the kidneys with extensive intracellular and intraluminal calcium oxalate monohydrate crystal depositions. PMID:26889430

  20. 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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  1. A novel method for determination of low molecular weight dicarboxylic acids in background atmospheric aerosol using ion chromatography.

    PubMed

    Tsai, Ying I; Hsieh, Li-Ying; Weng, Tzu-Hsiang; Ma, Yu-Chien; Kuo, Su-Ching

    2008-09-19

    This paper describes a novel gradient elution ion chromatographic method using a Dionex AS11 system for the determination of low molecular weight dicarboxylic acids (low-M(w) DCAs) in background atmospheric aerosol. Interference with the oxalic acid peak from sulfate in background PM(2.5) aerosol, 15.8 times the oxalic acid concentration, was remedied by removing sulfate using a barium cartridge, whilst interference with the malonic acid peak from carbonate was reduced by using a carbonate removal device. An alternative remedy to sulfate interference was use of an AS14 system using isocratic eluent, and this produced good resolution of oxalic acid from a high sulfate peak. In both the AS11 and the AS14 system, linear correlation coefficients were at all times >0.9990 with excellent linear range, the recoveries ranged from 92.8 to 106%, with relative standard deviation of 3.67-6.30%, whilst method detection limits (MDLs) ranged from 0.36microgL(-1) for malic acid to 3.87microgL(-1) for maleic acid. These data indicate that the analytical methods developed herein produce excellent separation efficiency and good determination of low-M(w) DCAs with satisfactory accuracy, recoveries, and MDLs. Samples left at room temperature (20 degrees C) for 300min in a simulation of the 'waiting time' involved in the proposed IC analysis decayed to between 86% (oxalic acid) and 39% (succinic and malonic acids) of their original concentration, whilst at 4 degrees C concentrations remained at 96-101% of original, indicating that maintaining samples at a low temperature prior to injection into the IC analyzer is vital for obtaining accurate results when analyzing low-M(w) DCAs. Oxalic acid was found to be the most prevalent low-M(w) DCA in background aerosol, comprising 57% of the total low-M(w) DCAs and 0.959% of the PM(2.5) aerosol mass, followed by succinic acid and malonic acid.

  2. Evaluation of Oxalate Concentration in the U.S. Spinach Germplasm Collection

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In addition to its high nutrient content, spinach (Spinacia oleracea L.) is also known to have greater amount of oxalic acid than most crops. Oxalic acid may form crystals with minerals to reduce the bioavailability and absorption of calcium and iron in diets, and calcium oxalate may deposit in the...

  3. Theoretical description of hydrogen bonding in oxalic acid dimer and trimer based on the combined extended-transition-state energy decomposition analysis and natural orbitals for chemical valence (ETS-NOCV)

    PubMed Central

    Mitoraj, Mariusz P.; Kurczab, Rafał; Boczar, Marek

    2010-01-01

    In the present study we have analyzed hydrogen bonding in dimer and trimer of oxalic acid, based on a recently proposed charge and energy decomposition scheme (ETS-NOCV). In the case of a dimer, two conformations, α and β, were considered. The deformation density contributions originating from NOCV’s revealed that the formation of hydrogen bonding is associated with the electronic charge deformation in both the σ—(Δρσ) and π-networks (Δρπ). It was demonstrated that σ-donation is realized by electron transfer from the lone pair of oxygen on one monomer into the empty \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \\rho_{H - O}^* $$\\end{document} orbital of the second oxalic acid fragment. In addition, a covalent contribution is observed by the density transfer from hydrogen of H-O group in one oxalic acid monomer to the oxygen atom of the second fragment. The resonance assisted component (Δρπ), is based on the transfer of electron density from the π—orbital localized on the oxygen of OH on one oxalic acid monomer to the oxygen atom of the other fragment. ETS-NOCV allowed to conclude that the σ(O---HO) component is roughly eight times as important as π (RAHB) contribution in terms of energetic estimation. The electrostatic factor (ΔEelstat) is equally as important as orbital interaction term (ΔEorb). Finally, comparing β-dimer of oxalic acid with trimer we found practically no difference concerning each of the O---HO bonds, neither qualitative nor quantitative. Figure The contours of deformation density σ- and π-contributions describing the hydrogen bonding between the monomers in the oxalic acid dimer, together with the corresponding ETS-NOCV-based orbital-interaction energies (in kcal/mol). PMID:20505966

  4. Determination of uric acid in urine, saliva and calcium oxalate renal calculi by high-performance liquid chromatography/mass spectrometry.

    PubMed

    Perelló, Joan; Sanchis, Pilar; Grases, Félix

    2005-09-25

    A very simple and direct method for determination of uric acid, in various biological matrices, based on high-performance liquid chromatography and mass spectrometry is described. Chromatographic separations were performed with a stationary phase Zorbax Sax Column, an anion exchange resin, with 50% sodium citrate 1 mM at pH 6.5 and 50% acetonitrile as mobile phase delivered at a flow rate of 1 ml/min. The detector counted negative ions by monitoring m/z 167.1, which corresponds to the urate anion. The method does not use an internal standard but quality control samples were used. Intra-day precision ranged between 1.1 and 1.5%, whereas inter-day precision was between 1.3 and 2.8% (n=5) working with some selected standards. Recovery tests of added standard have been successfully performed in urine and saliva samples, thus showing an appropriate accuracy of the method. The limit of quantitation found was 70 microg/l. Different urine and saliva samples were analyzed using an alternative analytical methodology based on an enzymatic reaction and photometric detection at 520 nm, resulting both methods comparable at a 95% confidence level. The method has been also applied to the determination of trace amounts of uric acid in the core of some selected calcium oxalate renal calculi. PMID:16061429

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

    SciTech Connect

    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.

  6. Novel one-pot synthesis of dicarboxylic acids mediated alginate-zirconium biopolymeric complex for defluoridation of water.

    PubMed

    Prabhu, Subbaiah Muthu; Meenakshi, Sankaran

    2015-04-20

    The present investigation explains the fluoride removal from aqueous solution using alginate-zirconium complex prepared with respective dicarboxylic acids like oxalic acid (Ox), malonic acid (MA) and succinic acid (SA) as a medium. The complexes viz., alginate-oxalic acid-zirconium (Alg-Ox-Zr), alginate-malonic acid-zirconium (Alg-MA-Zr) and alginate-succinic acid-zirconium (Alg-SA-Zr) were synthesized and studied for fluoride removal. The synthesized complexes were characterized by FTIR, XRD, SEM with EDAX and mapping images. The effects of various operating parameters were optimized. The result showed that the maximum removal of fluoride 9653mgF(-)/kg was achieved by Alg-Ox-Zr complex at acidic pH in an ambient atmospheric condition. Equilibrium data of Alg-Ox-Zr complex was fitted well with Freundlich isotherm. The calculated values of thermodynamic parameters indicated that the fluoride adsorption is spontaneous and endothermic in nature. The mechanism of fluoride removal behind Alg-Ox-Zr complex has been proposed in detail. The suitability of the Alg-Ox-Zr complex has been tested with the field sample collected in a nearby fluoride endemic area.

  7. A one-pot gold seed-assisted synthesis of gold/platinum wire nanoassemblies and their enhanced electrocatalytic activity for the oxidation of oxalic acid

    NASA Astrophysics Data System (ADS)

    Bai, Juan; Fang, Chun-Long; Liu, Zong-Huai; Chen, Yu

    2016-01-01

    Three-dimensional (3D) noble metal nanoassemblies composed of one-dimensional (1D) nanowires have been attracting much interest due to the unique physical and chemical properties of 1D nanowires as well as the particular interconnected open-pore structure of 3D nanoassemblies. In this work, well-defined Au/Pt wire nanoassemblies were synthesized by using a facile NaBH4 reduction method in the presence of a branched form of polyethyleneimine (PEI). A study of the growth mechanism indicated the morphology of the final product to be highly related to the molecular structure of the polymeric amine. Also, the preferred Pt-on-Pt deposition contributed to the formation of the 1D Pt nanowires. The Au/Pt wire nanoassemblies were functionalized with PEI at the same time that these nanoassemblies were synthesized due to the strong N-Pt bond. The chemically functionalized Au/Pt wire nanoassemblies exhibited better electrocatalytic activity for the electro-oxidation of oxalic acid than did commercial Pt black.Three-dimensional (3D) noble metal nanoassemblies composed of one-dimensional (1D) nanowires have been attracting much interest due to the unique physical and chemical properties of 1D nanowires as well as the particular interconnected open-pore structure of 3D nanoassemblies. In this work, well-defined Au/Pt wire nanoassemblies were synthesized by using a facile NaBH4 reduction method in the presence of a branched form of polyethyleneimine (PEI). A study of the growth mechanism indicated the morphology of the final product to be highly related to the molecular structure of the polymeric amine. Also, the preferred Pt-on-Pt deposition contributed to the formation of the 1D Pt nanowires. The Au/Pt wire nanoassemblies were functionalized with PEI at the same time that these nanoassemblies were synthesized due to the strong N-Pt bond. The chemically functionalized Au/Pt wire nanoassemblies exhibited better electrocatalytic activity for the electro-oxidation of oxalic acid than

  8. Metal- and anion-directed assemblies of CuII, CoII, NiII, and ZnII coordination polymers based on a bent dipyridyl ligand 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole and malonic acid

    NASA Astrophysics Data System (ADS)

    Jiang, Cheng-Hui; Qi, Yan-Mei; Sun, Yu; Chi, Qin; Guo, Ya-Mei

    2012-06-01

    This work presents six CuII, CoII, NiII, and ZnII coordination polymers assembled from a bent dipyridyl ligand 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt) and malonic acid (H2mal), which have been prepared at ambient conditions in water-methanol solution. Single-crystal X-ray diffraction indicates that these complexes show a variety of 1-D (for 2-6) and 2-D (for 1) coordination patterns. The results evidently reveal the versatility of 3-bpt with different configurations and binding modes in coordination assemblies, which will be profoundly influenced by the metal ions and even inorganic counter anions. Furthermore, extended supramolecular architectures are constructed via multiple secondary interactions such as hydrogen bonding and aromatic stacking.

  9. Malonate inhibits virulence gene expression in Vibrio cholerae.

    PubMed

    Minato, Yusuke; Fassio, Sara R; Häse, Claudia C

    2013-01-01

    We previously found that inhibition of the TCA cycle, either through mutations or chemical inhibition, increased toxT transcription in Vibrio cholerae. In this study, we found that the addition of malonate, an inhibitor of succinate dehydrogenase (SDH), decreased toxT transcription in V. cholerae, an observation inconsistent with the previous pattern observed. Unlike another SDH inhibitor, 2-thenoyltrifluoroacetone (TTFA), which increased toxT transcription and slightly inhibited V. cholerae growth, malonate inhibited toxT transcription in both the wild-type strain and TCA cycle mutants, suggesting malonate-mediated inhibition of virulence gene expression is independent to TCA cycle activity. Addition of malonate also inhibited ctxB and tcpA expressions but did not affect aphA, aphB, tcpP and toxR expressions. Malonate inhibited cholera toxin (CT) production in both V. cholerae classical biotype strains O395N1 and CA401, and El Tor biotype strain, N16961. Consistent with previous reports, we confirmed that these strains of V. cholerae did not utilize malonate as a primary carbon source. However, we found that the addition of malonate to the growth medium stimulated V. cholerae growth. All together, these results suggest that metabolizing malonate as a nutrient source negatively affects virulence gene expression in V. cholerae.

  10. Reduction of Oxalate Levels in Tomato Fruit and Consequent Metabolic Remodeling Following Overexpression of a Fungal Oxalate Decarboxylase1[W

    PubMed Central

    Chakraborty, Niranjan; Ghosh, Rajgourab; Ghosh, Sudip; Narula, Kanika; Tayal, Rajul; Datta, Asis; Chakraborty, Subhra

    2013-01-01

    The plant metabolite oxalic acid is increasingly recognized as a food toxin with negative effects on human nutrition. Decarboxylative degradation of oxalic acid is catalyzed, in a substrate-specific reaction, by oxalate decarboxylase (OXDC), forming formic acid and carbon dioxide. Attempts to date to reduce oxalic acid levels and to understand the biological significance of OXDC in crop plants have met with little success. To investigate the role of OXDC and the metabolic consequences of oxalate down-regulation in a heterotrophic, oxalic acid-accumulating fruit, we generated transgenic tomato (Solanum lycopersicum) plants expressing an OXDC (FvOXDC) from the fungus Flammulina velutipes specifically in the fruit. These E8.2-OXDC fruit showed up to a 90% reduction in oxalate content, which correlated with concomitant increases in calcium, iron, and citrate. Expression of OXDC affected neither carbon dioxide assimilation rates nor resulted in any detectable morphological differences in the transgenic plants. Comparative proteomic analysis suggested that metabolic remodeling was associated with the decrease in oxalate content in transgenic fruit. Examination of the E8.2-OXDC fruit proteome revealed that OXDC-responsive proteins involved in metabolism and stress responses represented the most substantially up- and down-regulated categories, respectively, in the transgenic fruit, compared with those of wild-type plants. Collectively, our study provides insights into OXDC-regulated metabolic networks and may provide a widely applicable strategy for enhancing crop nutritional value. PMID:23482874

  11. ADVANCED OXIDATION: OXALATE DECOMPOSITION TESTING WITH OZONE

    SciTech Connect

    Ketusky, E.; Subramanian, K.

    2012-02-29

    At the Savannah River Site (SRS), oxalic acid is currently considered the preferred agent for chemically cleaning the large underground Liquid Radioactive Waste Tanks. It is applied only in the final stages of emptying a tank when generally less than 5,000 kg of waste solids remain, and slurrying based removal methods are no-longer effective. The use of oxalic acid is preferred because of its combined dissolution and chelating properties, as well as the fact that corrosion to the carbon steel tank walls can be controlled. Although oxalic acid is the preferred agent, there are significant potential downstream impacts. Impacts include: (1) Degraded evaporator operation; (2) Resultant oxalate precipitates taking away critically needed operating volume; and (3) Eventual creation of significant volumes of additional feed to salt processing. As an alternative to dealing with the downstream impacts, oxalate decomposition using variations of ozone based Advanced Oxidation Process (AOP) were investigated. In general AOPs use ozone or peroxide and a catalyst to create hydroxyl radicals. Hydroxyl radicals have among the highest oxidation potentials, and are commonly used to decompose organics. Although oxalate is considered among the most difficult organic to decompose, the ability of hydroxyl radicals to decompose oxalate is considered to be well demonstrated. In addition, as AOPs are considered to be 'green' their use enables any net chemical additions to the waste to be minimized. In order to test the ability to decompose the oxalate and determine the decomposition rates, a test rig was designed, where 10 vol% ozone would be educted into a spent oxalic acid decomposition loop, with the loop maintained at 70 C and recirculated at 40L/min. Each of the spent oxalic acid streams would be created from three oxalic acid strikes of an F-area simulant (i.e., Purex = high Fe/Al concentration) and H-area simulant (i.e., H area modified Purex = high Al/Fe concentration) after nearing

  12. A novel digestion method based on a choline chloride-oxalic acid deep eutectic solvent for determining Cu, Fe, and Zn in fish samples.

    PubMed

    Habibi, Emadaldin; Ghanemi, Kamal; Fallah-Mehrjardi, Mehdi; Dadolahi-Sohrab, Ali

    2013-01-31

    A novel and efficient digestion method based on choline chloride-oxalic acid (ChCl-Ox) deep eutectic solvent (DES) was developed for flame atomic absorption spectrometry (FAAS) determination of Cu, Zn, and Fe in biological fish samples. Key parameters that influence analyte recovery were investigated and optimized, using the fish protein certified reference material (CRM, DORM-3) throughout the procedure. In this method, 100 mg of the sample was dissolved in ChCl-Ox (1:2, molar ratio) at 100°C for 45 min. Then, 5.0 mL HNO(3) (1.0 M) was added. After centrifugation, the supernatant solution was filtered, diluted to a known volume, and analyzed by FAAS. Under optimized conditions, an excellent agreement between the obtained results and the certified values was observed, using Student's t-test (P=0.05); the extraction recovery of the all elements was greater than 95.3%. The proposed method was successfully applied to the determination of analytes in different tissues (muscle, liver, and gills) having a broad concentration range in a marine fish sample. The reproducibility of the method was validated by analyzing all samples by our method in a different laboratory, using inductively coupled plasma optical emission spectrometry (ICP-OES). For comparison, a conventional acid digestion (CAD) method was also used for the determination of analytes in all studied samples. The simplicity of the proposed experimental procedure, high extraction efficiency, short analysis time, lack of concentrated acids and oxidizing agents, and the use of safe and inexpensive components demonstrate the high potential of ChCl-Ox (1:2) for routine trace metal analysis in biological samples.

  13. A novel digestion method based on a choline chloride-oxalic acid deep eutectic solvent for determining Cu, Fe, and Zn in fish samples.

    PubMed

    Habibi, Emadaldin; Ghanemi, Kamal; Fallah-Mehrjardi, Mehdi; Dadolahi-Sohrab, Ali

    2013-01-31

    A novel and efficient digestion method based on choline chloride-oxalic acid (ChCl-Ox) deep eutectic solvent (DES) was developed for flame atomic absorption spectrometry (FAAS) determination of Cu, Zn, and Fe in biological fish samples. Key parameters that influence analyte recovery were investigated and optimized, using the fish protein certified reference material (CRM, DORM-3) throughout the procedure. In this method, 100 mg of the sample was dissolved in ChCl-Ox (1:2, molar ratio) at 100°C for 45 min. Then, 5.0 mL HNO(3) (1.0 M) was added. After centrifugation, the supernatant solution was filtered, diluted to a known volume, and analyzed by FAAS. Under optimized conditions, an excellent agreement between the obtained results and the certified values was observed, using Student's t-test (P=0.05); the extraction recovery of the all elements was greater than 95.3%. The proposed method was successfully applied to the determination of analytes in different tissues (muscle, liver, and gills) having a broad concentration range in a marine fish sample. The reproducibility of the method was validated by analyzing all samples by our method in a different laboratory, using inductively coupled plasma optical emission spectrometry (ICP-OES). For comparison, a conventional acid digestion (CAD) method was also used for the determination of analytes in all studied samples. The simplicity of the proposed experimental procedure, high extraction efficiency, short analysis time, lack of concentrated acids and oxidizing agents, and the use of safe and inexpensive components demonstrate the high potential of ChCl-Ox (1:2) for routine trace metal analysis in biological samples. PMID:23327946

  14. Surface aggregation of urinary proteins and aspartic acid-rich peptides on the faces of calcium oxalate monohydrate investigated by in situ force microscopy

    SciTech Connect

    Weaver, M L; Qiu, S R; Hoyer, J R; Casey, W H; Nancollas, G H; De Yoreo, J J

    2008-05-28

    The growth of calcium oxalate monohydrate in the presence of Tamm-Horsfall protein (THP), osteopontin (OPN), and the 27-residue synthetic peptides (DDDS){sub 6}DDD and (DDDG){sub 6}DDD [where D = aspartic acid and X = S (serine) or G (glycine)] was investigated via in situ atomic force microscopy (AFM). The results show that these three growth modulators create extensive deposits on the crystal faces. Depending on the modulator and crystal face, these deposits can occur as discrete aggregates, filamentary structures, or uniform coatings. These proteinaceous films can lead to either the inhibition or increase of the step speeds (with respect to the impurity-free system) depending on a range of factors that include peptide or protein concentration, supersaturation and ionic strength. While THP and the linear peptides act, respectively, to exclusively increase and inhibit growth on the (-101) face, both exhibit dual functionality on the (010) face, inhibiting growth at low supersaturation or high modulator concentration and accelerating growth at high supersaturation or low modulator concentration. Based on analyses of growth morphologies and dependencies of step speeds on supersaturation and protein or peptide concentration, we argue for a picture of growth modulation that accounts for the observations in terms of the strength of binding to the surfaces and steps and the interplay of electrostatic and solvent-induced forces at crystal surface.

  15. CO2-free power generation on an iron group nanoalloy catalyst via selective oxidation of ethylene glycol to oxalic acid in alkaline media.

    PubMed

    Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

    2014-07-08

    An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

  16. Analysis of nanopore arrangement and structural features of anodic alumina layers formed by two-step anodizing in oxalic acid using the dedicated executable software

    NASA Astrophysics Data System (ADS)

    Zaraska, Leszek; Stępniowski, Wojciech J.; Sulka, Grzegorz D.; Ciepiela, Eryk; Jaskuła, Marian

    2014-02-01

    Anodic porous alumina layers were fabricated by a two-step self-organized anodization in 0.3 M oxalic acid under various anodizing potentials ranging from 30 to 60 V at two different temperatures (10 and 17 ∘C). The effect of anodizing conditions on structural features and pore arrangement of AAO was investigated in detail by using the dedicated executable publication combined with ImageJ software. With increasing anodizing potential, a linear increase of the average pore diameter, interpore distance, wall thickness and barrier layer thickness, as well as a decrease of the pore density, were observed. In addition, the higher pore diameter and porosity values were obtained for samples anodized at the elevated temperature, independently of the anodizing potential. A degree of pore order was investigated on the basis of Delaunay triangulations (defect maps) and calculation of pair distribution or angle distribution functions (PDF or ADF), respectively. All methods confirmed that in order to obtain nanoporous alumina with the best, hexagonal pore arrangement, the potential of 40 V should be applied during anodization. It was confirmed that the dedicated executable publication can be used to a fast and complex analysis of nanopore arrangement and structural features of nanoporous oxide layers.

  17. Expanding the applications of the ilmenite mineral to the preparation of nanostructures: TiO2 nanorods and their photocatalytic properties in the degradation of oxalic acid.

    PubMed

    Tao, Tao; Chen, Ying; Zhou, Dan; Zhang, Hongzhou; Liu, Sanly; Amal, Rose; Sharma, Neeraj; Glushenkov, Alexey M

    2013-01-14

    The mineral ilmenite is one of the most abundant ores in the Earth's crust and it is the main source for the industrial production of bulk titanium oxide. At the same time, methods to convert ilmenite into nanostructures of TiO(2) (which are required for new advanced applications, such as solar cells, batteries, and photocatalysts) have not been explored to any significant extent. Herein, we describe a simple and effective method for the preparation of rutile TiO(2) nanorods from ball-milled ilmenite. These nanorods have small dimensions (width: 5-20 nm, length: 50-100 nm, thickness: 2-5 nm) and possess large specific surface areas (up to 97 m(2)  g(-1)). Dissolution/hydrolysis/precipitation is proposed as a growth mechanism. The nanorods were found to have attractive photocatalytic properties in the degradation of oxalic acid. Their photocatalytic activity is close to that of the benchmark Degussa P25 material and better than that of a commercial high-surface-area rutile powder. PMID:23180682

  18. Heterogeneous catalysis by solid superacids--14. Perfluorinated resinsulfonic acid (nafion-h) catalyzed Friedel-crafts alkylation of toluene and phenol with alkyl chloroformates and oxalates

    SciTech Connect

    Olah, G.A.; Meidar, D.; Malhotra, R.; Olah, J.A.; Narang, S.C.

    1980-01-01

    Product distributions obtained in the alkylation of toluene with methyl, ethyl, and isopropyl chloroformate and dimethyl oxalate and of phenol with methyl and ethyl chloroformate and dimethyl- and diethyloxalate.

  19. Ascorbic acid decomposition into oxalate ions: a simple synthetic route towards oxalato-bridged heterometallic 3d-4f clusters.

    PubMed

    Dinca, Alina S; Shova, Sergiu; Ion, Adrian E; Maxim, Catalin; Lloret, Francesc; Julve, Miguel; Andruh, Marius

    2015-04-28

    Two types of oxalato-bridged heterometallic 3d-4f dodeca- and hexanuclear compounds have been obtained by connecting six bi- and, respectively, trinuclear moieties through oxalato bridges arising from the slow decomposition of the L-ascorbic acid.

  20. Synthesis and mesomorphic properties of calamitic malonates and cyanoacetates tethered to 4-cyanobiphenyls

    PubMed Central

    Kress, Katharina C; Kaller, Martin; Axenov, Kirill V; Tussetschläger, Stefan

    2012-01-01

    Summary 4-Cyano-1,1'-biphenyl derivatives bearing ω-hydroxyalkyl substituents were reacted with methyl 3-chloro-3-oxopropionate or cyanoacetic acid, giving liquid-crystalline linear malonates and cyanoacetates. These compounds formed monotropic nematic phases at 62 °C down to ambient temperature upon cooling from the isotropic liquid. The mesomorphic properties were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction (WAXS). PMID:22509205

  1. Alterations in circadian rhythmicity in calcium oxalate renal stone formers.

    PubMed

    Touitou, Y; Touitou, C; Charransol, G; Reinberg, A; Thomas, J; Bogdan, A; Barthelemy, C; Desgrez, P

    1983-01-01

    The circadian (circannual for oxalic acid) variations of 13 urinary variables (volume, creatinine, calcium, oxalic acid, glycolic acid, 17-ketosteroids, 17-hydroxycorticosteroids, phosphates, urea, uric acid, chloride, sodium, and potassium) have been documented in 7 calcium oxalate renal stone formers and 7 healthy men (control group). Urine was collected every 4 h over a period of 24 h. All subjects had the same synchronization: diurnal activity from 07(00) to 23(00) +/- 1 h and nocturnal rest; meals were given at fixed clock hours (08(00), 12(30) and 20(00) +/- 1 h). A statistically-significant rhythm (p less than 0.05) was validated for all variables except urea and calcium in healthy men. In renal stone formers, 6 variables (calcium, oxalic acid, and glycolic acid in particular) had no detectable circadian rhythm. However, a periodicity of c. 8 h (ultradian rhythm) was demonstrated for calcium and oxalic acid with peaks being located around 02(00), 10(00), and 18(00). No circannual variations in oxalic acid output could be observed. The present study shows an alteration of the periodicity of calcium and oxalic metabolisms, i.e. the loss of a circadian (24-h) rhythm and the occurrence of an ultradian rhythm of 8 h. The risk of calcium-oxalate crystallisation appears thus greater at 02(00), 10(00), and 18(00). Furthermore, any study dealing with oxalic acid excretion should state the season of urine collection when comparing renal stone formers and healthy subjects, as significant differences in oxaluria may appear during the summer months and not during the rest of the year. PMID:6862698

  2. THORIUM OXALATE-URANYL ACETATE COUPLED PROCEDURE FOR THE SEPARATION OF RADIOACTIVE MATERIALS

    DOEpatents

    Gofman, J.W.

    1959-08-11

    The recovery of fission products from neutronirradiated uranium is described. The neutron-irradiated uranium is dissolved in acid and thorium oxalate is precipitated in ihe solution formed, whereby the fission products are carried on the thorium oxalate. The separated thorium oxalate precipitate is then dissolved in an aqueous oxalate solution and the solution formed is acidified, limiting ihe excess acidity to a maximum of 2 N, whereby thorium oxalate precipitates and carries lanthanum-rareearth- and alkaline-earth-metal fission products while the zirconium-fission-product remains in solution. This precipitate, too, is dissolved in an aqaeous oxalate solution at elevated temperature, and lanthanum-rare-earth ions are added to the solution whereby lanthanum-rare-earth oxalate forms and the lanthanum-rare-earth-type and alkalineearth-metal-type fission products are carried on the oxalate. The precipitate is separated from the solution.

  3. PREPARATION OF OXALATES OF METALS OF ATOMIC NUMBER GREATER THAN 88

    DOEpatents

    Duffield, R.B.

    1959-02-01

    A method is presented for the preparation of oxalates of metals of atomic number greater than 88. A solid peroxide of the heavy metal is contacted with an aqueous oxalic acid solution ai a temperature of about 50 C for a period of time sufficient to form the insoluble metal oxalate which is subsequentiy recovered as a pures crystalline compound.

  4. Ultra-structural mapping of sugarcane bagasse after oxalic acid fiber expansion (OAFEX) and ethanol production by Candida shehatae and Saccharomyces cerevisiae

    PubMed Central

    2013-01-01

    Background Diminishing supplies of fossil fuels and oil spills are rousing to explore the alternative sources of energy that can be produced from non-food/feed-based substrates. Due to its abundance, sugarcane bagasse (SB) could be a model substrate for the second-generation biofuel cellulosic ethanol. However, the efficient bioconversion of SB remains a challenge for the commercial production of cellulosic ethanol. We hypothesized that oxalic-acid-mediated thermochemical pretreatment (OAFEX) would overcome the native recalcitrance of SB by enhancing the cellulase amenability toward the embedded cellulosic microfibrils. Results OAFEX treatment revealed the solubilization of hemicellulose releasing sugars (12.56 g/l xylose and 1.85 g/l glucose), leaving cellulignin in an accessible form for enzymatic hydrolysis. The highest hydrolytic efficiency (66.51%) of cellulignin was achieved by enzymatic hydrolysis (Celluclast 1.5 L and Novozym 188). The ultrastructure characterization of SB using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy, Fourier transform–near infrared spectroscopy (FT-NIR), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) revealed structural differences before and after OAFEX treatment with enzymatic hydrolysis. Furthermore, fermentation mediated by C. shehatae UFMG HM52.2 and S. cerevisiae 174 showed fuel ethanol production from detoxified acid (3.2 g/l, yield 0.353 g/g; 0.52 g/l, yield, 0.246 g/g) and enzymatic hydrolysates (4.83 g/l, yield, 0.28 g/g; 6.6 g/l, yield 0.46 g/g). Conclusions OAFEX treatment revealed marked hemicellulose degradation, improving the cellulases’ ability to access the cellulignin and release fermentable sugars from the pretreated substrate. The ultrastructure of SB after OAFEX and enzymatic hydrolysis of cellulignin established thorough insights at the molecular level. PMID:23324164

  5. Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water.

    PubMed

    Tong, Shaoping; Shi, Rui; Zhang, Hua; Ma, Chunan

    2010-01-01

    Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3)3 x 9H2O and Co(NO3)2 x 6H2O as the precursors, and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy)propionic acid (2,4-DP), nitrobenzene and oxalic acid. The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation efficiency during the degradation of each organic pollutant, and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism. The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance. In the catalytic ozonation of 2,4-DP, the apparent reaction rate constants (k) were determined to be 1.456 x 10(-2) min(-1) for ozonation alone and 4.740 x 10(-2) min(-1) for O3/Fe3O4-CoO/Al203. And O3/Fe3O4-CoO/Al2O3 had a larger R(ct) (6.614 x 10(-9)) calculated by the relative method than O3 did (1.800 x 10(-9)), showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical. Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid. The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree. PMID:21235195

  6. Biochemical, molecular and outcome analysis of eight chinese asymptomatic individuals with methyl malonic acidemia detected through newborn screening.

    PubMed

    Han, Lianshu; Wu, Shengnan; Ye, Jun; Qiu, Wenjuan; Zhang, Huiwen; Gao, Xiaolan; Wang, Yu; Gong, Zhuwen; Jin, Jing; Gu, Xuefan

    2015-10-01

    Methyl malonic academia (MMA) is characterized by abnormal accumulation of methyl malonic acid in body fluids. Patients usually have a variety of clinical symptoms including recurrent vomiting, metabolic acidosis, developmental delay, seizure, or death. However, a few cases where the patients have no symptom are also reported. Here, we conducted clinical, biochemical, and molecular analysis of eight Chinese patients identified through newborn screening between 2003 and 2013. All the patients had significantly higher blood propionylcarnitine (C3) concentrations, ratio of propionylcarnitine/acetylcarnitine (C3/C2); and their urine methyl malonic acid and methylcitric acid (MCA) excretions were remarkably higher than normal at diagnosis and during follow-ups. In addition, five different known mutations were identified in seven of the eight patients in either MUT or MMACHC. All these mutations were expected to produce defective proteins that would result in decreased or even total loss of methyl malonyl-CoA mutase activity. However, normal outcomes were found in all patients in physical growth, intellectual performance and cerebral MRI analysis at diagnosis (range, 14-53 days) and during follow-ups (range, 1.8-10 years). Our study is the first report of Chinese MMA patients with increased secretion of methyl malonic acid and molecular defects in MUT or MMACHC yet remain asymptomatic. PMID:25982642

  7. Carboxylic acids in PM 2.5 over Pinus morrisonicola forest and related photoreaction mechanisms identified via Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Kuo, Su-Ching; Tsai, Ying I.; Tsai, Cheng-Hsien; Hsieh, Li-Ying

    2011-12-01

    The PM 2.5 aerosol from within an area of Pinus morrisonicola Hayata in Taiwan was collected and analyzed for its low molecular weight carboxylic acid (LMWCAs) content. Oxalic acid was the major LMWCA in the aerosol, followed by acetic, tartaric and maleic acids. This differs significantly from the LMWCA composition of PM 2.5 aerosol reported for a southern Taiwan suburban region (oxalic > succinic > malonic) [Atmospheric Environment 42, 6836-6850 (2008)]. P. morrisonicola Hayata emits oxalic, malic and formic acids and yet there was an abundance of maleic and tartaric acids in the PM 2.5 forest aerosol, indicating that tartaric acid is derived from the transformation of other P. morrisonicola Hayata emissions. Raman spectroscopy was applied and 28 species of LMWCAs and inorganic species were identified. The photochemical mechanisms of maleic and tartaric acids were studied and it was found that the abundant tartaric acid in forest aerosol is most probably the photochemical product from reactions of maleic acid. Furthermore, tartaric acid is photochemically transformed into formic acid and ultimately into CO 2.

  8. Optical properties in the UV and visible spectral region of organic acids relevant to tropospheric aerosols

    NASA Astrophysics Data System (ADS)

    Lund Myhre, C. E.; Nielsen, C. J.

    2004-09-01

    Refractive and absorption indices in the UV and visible region of selected aqueous organic acids relevant to tropospheric aerosols are reported. The acids investigated are the aliphatic dicarboxylic acids oxalic, malonic, tartronic, succinic and glutaric acid. In addition we report data for pyruvic, pinonic, benzoic and phthalic acid. To cover a wide range of conditions we have investigated the aqueous organic acids at different concentrations spanning from highly diluted samples to concentrations close to saturation. The density of the investigated samples is reported and a parameterisation of the absorption and refractive index that allows the calculation of the optical constants of mixed aqueous organic acids at different concentrations is presented. The single scattering albedo is calculated for two size distributions using measured and a synthetic set of optical constants. The results show that tropospheric aerosols consisting of only these organic acids and water have a pure scattering effect.

  9. Optical properties in the UV and visible spectral region of organic acids relevant to tropospheric aerosols

    NASA Astrophysics Data System (ADS)

    Lund Myhre, C. E.; Nielsen, C. J.

    2004-06-01

    Refractive and absorption indices in the UV and visible region of selected aqueous organic acids relevant to tropospheric aerosols are reported. The acids investigated are the aliphatic dicarboxylic acids oxalic, malonic, tartronic, succinic and glutaric acid. In addition we report data for pyruvic, pinonic, benzoic and phthalic acid. To cover a wide range of conditions we have investigated the aqueous organic acids at different concentrations spanning from highly diluted samples to concentrations close to saturation. The density of the investigated samples is reported and a parameterisation of the absorption and refractive index that allows the calculation of the optical constants of mixed aqueous organic acids at different concentrations is presented. The single scattering albedo is calculated for two size distributions using measured and a synthetic set of optical constants. The results show that tropospheric aerosols consisting of only these organic acids and water have a pure scattering effect.

  10. Efficient electron-induced removal of oxalate ions and formation of copper nanoparticles from copper(II) oxalate precursor layers

    PubMed Central

    Rückriem, Kai; Grotheer, Sarah; Vieker, Henning; Penner, Paul; Beyer, André; Gölzhäuser, Armin

    2016-01-01

    Summary Copper(II) oxalate grown on carboxy-terminated self-assembled monolayers (SAM) using a step-by-step approach was used as precursor for the electron-induced synthesis of surface-supported copper nanoparticles. The precursor material was deposited by dipping the surfaces alternately in ethanolic solutions of copper(II) acetate and oxalic acid with intermediate thorough rinsing steps. The deposition of copper(II) oxalate and the efficient electron-induced removal of the oxalate ions was monitored by reflection absorption infrared spectroscopy (RAIRS). Helium ion microscopy (HIM) reveals the formation of spherical nanoparticles with well-defined size and X-ray photoelectron spectroscopy (XPS) confirms their metallic nature. Continued irradiation after depletion of oxalate does not lead to further particle growth giving evidence that nanoparticle formation is primarily controlled by the available amount of precursor. PMID:27547602

  11. Efficient electron-induced removal of oxalate ions and formation of copper nanoparticles from copper(II) oxalate precursor layers.

    PubMed

    Rückriem, Kai; Grotheer, Sarah; Vieker, Henning; Penner, Paul; Beyer, André; Gölzhäuser, Armin; Swiderek, Petra

    2016-01-01

    Copper(II) oxalate grown on carboxy-terminated self-assembled monolayers (SAM) using a step-by-step approach was used as precursor for the electron-induced synthesis of surface-supported copper nanoparticles. The precursor material was deposited by dipping the surfaces alternately in ethanolic solutions of copper(II) acetate and oxalic acid with intermediate thorough rinsing steps. The deposition of copper(II) oxalate and the efficient electron-induced removal of the oxalate ions was monitored by reflection absorption infrared spectroscopy (RAIRS). Helium ion microscopy (HIM) reveals the formation of spherical nanoparticles with well-defined size and X-ray photoelectron spectroscopy (XPS) confirms their metallic nature. Continued irradiation after depletion of oxalate does not lead to further particle growth giving evidence that nanoparticle formation is primarily controlled by the available amount of precursor. PMID:27547602

  12. [Determination of organic acids and inorganic anions by gradient ion chromatography].

    PubMed

    Liu, Z; Liu, K; Shen, D; Song, Q; Mou, S; Feng, Y

    1997-07-01

    The chromatographic conditions for separation and detection of organic acids and inorganic anions by gradient ion chromatography with suppressed conductivity detection were studied. The optimized gradient programs were established. Ion chromatography were performed with a DX-100 chromatograph (DIONEX). The separation column is IonPac-AS11. Compared with NaHCO3/Na2CO3 and Na2B4O7, NaOH was the optimal eluent. The effect of organic modifier was also studied. Among methanol, 2-propanol and acetonitrile, methanol can make ion pairs such as malate and succinate, malonate and tartrate gaining baseline resolution. By using ion exchange separation, Cl-, NO3-, malate, succinate, malonate, tartrate, SO4(2-), oxalate were eluted between 5 mmol/L NaOH-16% CH3OH and 10 mmol/L NaOH-16% CH3OH in 25 min. A mobile phase composed of 30 mmol/L NaOH, 50% CH3OH and D.I. water was chosen to elute two groups of organic acids and inorganic anions: (1) quinate, formate, Cl-, malate, malonate, oxalate, citrate, isocitrate, aconitate; (2) lactate, Cl-, SO4(2-), tartrate, PO4(3-), citrate, isocitrate, aconitate. The detection limits (S/N = 3) were 0.1625 (quinate), 0.0691 (formate), 0.0115 (Cl-), 0.0886 (malate), 0.0591 (malonate), 0.0263 (oxalate), 0.1147 (citrate), 0.2017 (isocitrate), 0.3656 (cis-aconitate), 0.1045 (trans-aconitate), 0.1950 (lactate), 0.0729 (tartrate), 0.0224 (SO4(2-)) and 0.0692 (PO4(3-)) mg/L. The relative standard deviations were lower than 11.9% (n = 7) and the correlation coefficients ranged from 0.9212 for Cl- to 0.9999 for formate. The method was applied to determine the organic acids and inorganic anions of beverages and citric acids fermenting-medium. The results were satisfactory.

  13. 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

    SciTech Connect

    Hou, Juan-Juan; Xu, Xia; Jiang, Ning; Wu, Ya-Qin; Zhang, Xian-Ming

    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 3D 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.

  14. The influence of magnesium chloride on blood and urine parameters in calcium oxalate stone patients.

    PubMed

    Brundig, P; Berg, W; Schneider, H J

    1981-01-01

    The influence of magnesium chloride on various blood and urine parameters in calcium oxalate stone patients is studied. High dose magnesium therapy was found to increase urinary magnesium concentrations, whereas the oxalic acid concentration is reduced. The experiments support the statements on the role of magnesium in endogenous oxalic acid depression and the inhibition of the intestinal resorption. For urolith prevention it will be necessary to apply high magnesium doses of easily absorbable and well-tolerated medicaments.

  15. Biogeochemistry of oxalate in the antarctic cryptoendolithic lichen-dominated community.

    PubMed

    Johnston, C G; Vestal, J R

    1993-05-01

    Cryptoendolithic (hidden in rock) lichen-dominated microbial communities from the Ross Desert of Antarctica were shown to produce oxalate (oxalic acid). Oxalate increased mineral dissolution, which provides nutrients, creates characteristic weathering patterns, and may ultimately influence the biological residence time of the community. Oxalate was the only organic acid detectable by HPLC, and its presence was verified by GC/MS. Community photosynthetic metabolism was involved in oxalate production since rates of (14)C-oxalate production from (14)C02 were higher in light than in dark incubations. Flaking of the sandstone at the level of the lichen-dominated zone a few millimeters beneath the rock surface can be explained by dissolution of the sandstone cement, which was enhanced by Si, Fe, and Al oxalate complex formation. Added oxalate was observed to increase the solubility of Si, Fe, Al, P, and K. Oxalate's ability to form soluble trivalent metal-oxalate complexes correlated with the observed order of metal oxide depletion from the lichen-dominated zone (Mn > Fe > Al). Thermodynamic calculations predict that Fe oxalate complex formation mobilizes amorphous Fe oxides (ferrihydrite) in the lichen-dominated zone, and where oxalate is depleted, ferrihydrite should precipitate. Hematite, a more crystalline Fe oxide, should remain solid at in situ oxalate concentrations. Oxalate was not a carbon source for the indigenous heterotrophs, but the microbiota were involved in oxalate mineralization to CO2, since oxalate mineralization was reduced in poisoned incubations. Photooxidation of oxalate to C02 coupled with photoreduction of Fe(Ill) may be responsible for oxalate removal in situ, since rates of (14)C-oxalate mineralization in dark incubations were at least 50% lower than those in the light. Removal of oxalate from Si, Fe, and Al complexes should allow free dissolved Si, Fe, and Al to precipitate as amorphous silicates and metal oxides. This may explain increased

  16. [The effect of sodium malonate on yeast thermotolerance].

    PubMed

    Rikhvanov, E G; Varakina, N N; Rusaleva, T M; Rachenko, E I; Voĭnikov, V K

    2003-01-01

    The study of the effect of malonate (an inhibitor of the succinate dehydrogenase complex of the respiratory chain of mitochondria) on the thermotolerance of the fermentative Saccharomyces cerevisiae and nonfermentative Rhodotorula rubra yeasts showed that malonate augmented the damaging effect of heat shock on the yeasts utilizing glucose (or other sugars) by means of oxidative phosphorylation. At the same time, malonate did not influence and sometimes even improved the thermotolerance of the yeasts utilizing glucose through fermentation. The suggestion is made that cell tolerance to heat shock depends on the normal functioning of mitochondria. On the other hand, their increased activity at elevated temperatures may accelerate the formation of cytotoxic reactive oxygen species and, hence, is not beneficial to cells.

  17. Genetic evidence for differences in the pathways of druse and prismatic calcium oxalate crystal formation in Medicago truncatula

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Current evidence supports a single pathway of oxalate biosynthesis utilising ascorbic acid as the precursor. In this study, we begin to address the possibility that more than one pathway of oxalate biosynthesis and calcium oxalate formation occurs in Medicago truncatula Gaertn. (cv. Jemalong genotyp...

  18. 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

    NASA Astrophysics Data System (ADS)

    Hou, Juan-Juan; Xu, Xia; Jiang, Ning; Wu, Ya-Qin; Zhang, Xian-Ming

    2015-03-01

    Solvothermal reactions of metal salts, 3-amino-1,2,4-triazole-5-carboxylic acid (H2atzc) and ammonium oxalate in different temperature produced two metal azolate frameworks, namely, [Cu3(atzc)2(atz)(ox)]·1.5H2O (1) and [Co5(atz)4(ox)3(HCOO)2]·DMF (2) (H2atzc=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 [Cu3(atzc)2(atz)]2- layers of mixed μ4-atzc and μ3-atz ligands, which are pillared by ox2- groups to form a 3D porous framework. Compound 2 contains 2D layers with basic spindle-shaped decanuclear units, which extended by ox2- and formates to form 3D porous framework. Gas adsorption investigation revealed that two kinds of frameworks exhibited selective CO2 over N2 sorption. Moreover, activated 2 shows H2 storage capacity. Additionally, magnetic properties of both the compounds have been investigated.

  19. Urinary oxalate and glycolate excretion and plasma oxalate concentration.

    PubMed Central

    Barratt, T M; Kasidas, G P; Murdoch, I; Rose, G A

    1991-01-01

    The diagnosis of primary hyperoxaluria in young children is hampered by the lack of a reliable reference range for urinary oxalate excretion, especially in infants. We present data on urinary oxalate and glycolate excretion in 137 normal children, on the plasma oxalate concentration in 33 normal children and 53 with chronic renal failure, and on amniotic fluid oxalate concentration in 63 uncomplicated pregnancies. The urinary oxalate:creatinine molar ratios were log normally distributed: mean (range) values were less than 1 year 0.061 (0.015-0.26), 1-5 years 0.036 (0.011-0.12), 5-12 years 0.030 (0.0059-0.15), and greater than 12 years 0.013 (0.0021-0.083). Geometric mean (range) plasma oxalate concentration in the normal children was 1.53 (0.78-3.02) mumols/l and was independent of age. The mean (SD) plasma oxalate: creatinine molar ratio in these normal children and 50 with chronic renal failure was 0.033 (0.013), and was independent of age and renal function. Mean (SD) amniotic fluid oxalate concentration was 19.0 (4.3) mumols/l. PMID:2031609

  20. Distribution of Components in Ion Exchange Materials Taken from the K East Basin and Leaching of Ion Exchange Materials by Nitric/Hydrofluoric Acid and Nitric/Oxalic Acid

    SciTech Connect

    Delegard, C.H.; Rinehart, D.E.; Hoopes, F.V.

    1999-04-02

    Laboratory tests were performed to examine the efficacy of mixed nitric/hydrofluoric acid followed by mixed nitric/oxalic acid leach treatments to decontaminate ion exchange materials that have been found in a number of samples retrieved from K East (KE)Basin sludge. The ion exchange materials contain organic ion exchange resins and zeolite inorganic ion exchange material. Based on process records, the ion exchange resins found in the K Basins is a mixed-bed, strong acid/strong base material marketed as Purolite NRW-037. The zeolite material is Zeolon-900, a granular material composed of the mineral mordenite. Radionuclides sorbed or associated with the ion exchange material can restrict its disposal to the Environmental Restoration Disposal Facility (ERDF). The need for testing to support development of a treatment process for K Basin sludge has been described in Section 4.2 of ''Testing Strategy to Support the Development of K Basins Sludge Treatment Process'' (Flament 1998). Elutriation and washing steps are designed to remove the organic resins from the K Basin sludge. To help understand the effects of the anticipated separation steps, tests were performed with well-rinsed ion exchange (IX) material from KE Basin floor sludge (sample H-08 BEAD G) and with well-rinsed IX having small quantities of added KE canister composite sludge (sample KECOMP). Tests also were performed to determine the relative quantities of organic and inorganic IX materials present in the H-08 K Basin sludge material. Based on chemical analyses of the separated fractions, the rinsed and dry IX material H-08 BEAD G was found to contain 36 weight percent inorganic material (primarily zeolite). The as-received (unrinsed) and dried H-08 material was estimated to contain 45 weight percent inorganic material.

  1. 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...

  2. USE OF AN EQUILIBRIUM MODEL TO FORECAST DISSOLUTION EFFECTIVENESS, SAFETY IMPACTS, AND DOWNSTREAM PROCESSABILITY FROM OXALIC ACID AIDED SLUDGE REMOVAL IN SAVANNAH RIVER SITE HIGH LEVEL WASTE TANKS 1-15

    SciTech Connect

    KETUSKY, EDWARD

    2005-10-31

    This thesis details a graduate research effort written to fulfill the Magister of Technologiae in Chemical Engineering requirements at the University of South Africa. The research evaluates the ability of equilibrium based software to forecast dissolution, evaluate safety impacts, and determine downstream processability changes associated with using oxalic acid solutions to dissolve sludge heels in Savannah River Site High Level Waste (HLW) Tanks 1-15. First, a dissolution model is constructed and validated. Coupled with a model, a material balance determines the fate of hypothetical worst-case sludge in the treatment and neutralization tanks during each chemical adjustment. Although sludge is dissolved, after neutralization more is created within HLW. An energy balance determines overpressurization and overheating to be unlikely. Corrosion induced hydrogen may overwhelm the purge ventilation. Limiting the heel volume treated/acid added and processing the solids through vitrification is preferred and should not significantly increase the number of glass canisters.

  3. Predictions of diagenetic reactions in the presence of organic acids

    NASA Astrophysics Data System (ADS)

    Harrison, Wendy J.; Thyne, Geoffrey D.

    1992-02-01

    Stability constants have been estimated for cation complexes with anions of monofunctional and difunctional acids (combinations of Ca, Mg, Fe, Al, Sr, Mn, U, Th, Pb, Cu, Zn with formate, acetate, propionate, oxalate, malonate, succinate, and salicylate) between 0 and 200°C. Difunctional acid anions form much more stable complexes than monofunctional acid anions with aluminum; the importance of the aluminum-acetate complex is relatively minor in comparison to aluminum oxalate and malonate complexes. Divalent metal cations such as Mg, Ca, and Fe form more stable complexes with acetate than with difunctional acid anions. Aluminum-oxalate can dominate the species distribution of aluminum under acidic pH conditions, whereas the divalent cation-acetate and oxalate complexes rarely account for more than 60% of the total dissolved cation, and then only in more alkaline waters. Mineral thermodynamic affinities were calculated using the reaction path model EQ3/6 for waters having variable organic acid anion (OAA) contents under conditions representative of those found during normal burial diagenesis. The following scenarios are possible: 1) K-feldspar and albite are stable, anorthite dissolves 2) All feldpars are stable 3) Carbonates can be very unstable to slightly unstable, but never increase in stability. Organic acid anions are ineffective at neutral to alkaline pH in modifying stabilities of aluminosilicate minerals whereas the anions are variably effective under a wide range of pH in modifying carbonate mineral stabilities. Reaction path calculations demonstrate that the sequence of mineral reactions occurring in an arkosic sandstone-fluid system is only slightly modified by the presence of OAA. A spectrum of possible sandstone alteration mineralogies can be obtained depending on the selected boundary conditions: EQ3/6 predictions include quartz overgrowth, calcite replacement of plagioclase, albitization of plagioclase, and the formation of porosity-occluding calcite

  4. Evidence for a cytoplasmic pathway of oxalate biosynthesis in Aspergillus niger

    SciTech Connect

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

    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 during 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.

  5. 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

    PubMed Central

    Foster, Justin; Luo, Bin; Nakata, Paul A.

    2016-01-01

    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 possess this activity. Recently, an Acyl Activating Enzyme 3 (AAE3), encoding an oxalyl-CoA synthetase, was identified in Arabidopsis. AAE3 has been proposed to catalyze the first step in an alternative pathway of oxalate degradation. Whether this enzyme and proposed pathway is important to other plants is unknown. Here, we identify the Medicago truncatula AAE3 (MtAAE3) and show that it encodes an oxalyl-CoA synthetase activity exhibiting high activity against oxalate with a Km = 81 ± 9 μM and Vmax = 19 ± 0.9 μmoles min-1mg protein-1. GFP-MtAAE3 localization suggested that this enzyme functions within the cytosol of the cell. Mtaae3 knock-down line showed a reduction in its ability to degrade oxalate into CO2. This reduction in the capacity to degrade oxalate resulted in the accumulation of druse crystals of calcium oxalate in the Mtaae3 knock-down line and an increased susceptibility to oxalate-secreting phytopathogens such as Sclerotinia sclerotiorum. Taken together, these results suggest that AAE3 dependent turnover of oxalate is important to different plants and functions in the regulation of tissue calcium oxalate crystal accumulation and in defense against oxalate-secreting phytopathogens. PMID:26900946

  6. Hygroscopic Behavior of Multicomponent Aerosols Involving NaCl and Dicarboxylic Acids.

    PubMed

    Peng, Chao; Jing, Bo; Guo, Yu-Cong; Zhang, Yun-Hong; Ge, Mao-Fa

    2016-02-25

    Atmospheric aerosols are usually complex mixtures of inorganic and organic compounds. The hygroscopicity of mixed particles is closely related to their chemical composition and interactions between components, which is still poorly understood. In this study, the hygroscopic properties of submicron particles composed of NaCl and dicarboxylic acids including oxalic acid (OA), malonic acid (MA), and succinic acid (SA) with various mass ratios are investigated with a hygroscopicity tandem differential mobility analyzer (HTDMA) system. Both the Zdanovskii-Stokes-Robinson (ZSR) method and extended aerosol inorganics model (E-AIM) are applied to predict the water uptake behaviors of sodium chloride/dicarboxylic acid mixtures. For NaCl/OA mixed particles, the measured growth factors were significantly lower than predictions from the model methods, indicating a change in particle composition caused by chloride depletion. The hygroscopic growth of NaCl/MA particles was well described by E-AIM, and that of NaCl/SA particles was dependent upon mixing ratio. Compared with model predictions, it was determined that water uptake of the NaCl/OA mixture could be enhanced and could be closer to the predictions by addition of levoglucosan or malonic acid, which retained water even at low relative humidity (RH), leading to inhibition of HCl evaporation during dehydration. These results demonstrate that the coexisting hygroscopic species have a strong influence on the phase state of particles, thus affecting chemical interactions between inorganic and organic compounds as well as the overall hygroscopicity of mixed particles. PMID:26820230

  7. Inactivation of malonate semialdehyde decarboxylase by 3-halopropiolates: evidence for hydratase activity.

    PubMed

    Poelarends, Gerrit J; Serrano, Hector; Johnson, William H; Whitman, Christian P

    2005-07-01

    Malonate semialdehyde decarboxylase (MSAD) from Pseudomonas pavonaceae 170 catalyzes the metal ion-independent decarboxylation of malonate semialdehyde and represents one of three known enzymatic activities in the tautomerase superfamily. The characterized members of this superfamily are structurally homologous proteins that share a beta-alpha-beta fold and a catalytic amino-terminal proline. Sequence analysis, chemical labeling studies, site-directed mutagenesis, and NMR studies of MSAD identified Pro-1 as a key active site residue in which the amino group has a pKa value of 9.2. The available evidence suggests a mechanism involving polarization of the C-3 carbonyl group of malonate semialdehyde by the cationic Pro-1. A second critical active site residue, Arg-75, could assist in the reaction by placing the substrate's carboxylate group in a favorable conformation for decarboxylation. In addition to the decarboxylase activity, MSAD has a hydratase activity as demonstrated by the MSAD-catalyzed conversion of 2-oxo-3-pentynoate to acetopyruvate. In view of this activity, MSAD was incubated with 3-bromo- and 3-chloropropiolate, and the subsequent reactions were characterized. Both compounds result in the irreversible inactivation of MSAD, making them the first identified inhibitors of MSAD. Inactivation by 3-chloropropiolate occurs in a time- and concentration-dependent manner and is due to the covalent modification of Pro-1. The proposed mechanism for inactivation involves the initial hydration of the 3-halopropiolate followed by a rearrangement to an alkylating agent, either an acyl halide or a ketene. The results provide additional evidence for the hydratase activity of MSAD and further support for the hypothesis that MSAD and trans-3-chloroacrylic acid dehalogenase, the preceding enzyme in the trans-1,3-dichloropropene catabolic pathway, diverged from a common ancestor but conserved the necessary catalytic machinery for the conjugate addition of water.

  8. Update on Oxalate Crystal Disease

    PubMed Central

    Lorenz, Elizabeth C.; Michet, Claude J.; Milliner, Dawn S.; Lieske, John C.

    2013-01-01

    Oxalate arthropathy is a rare cause of arthritis characterized by deposition of calcium oxalate crystals within synovial fluid. This condition typically occurs in patients with underlying primary or secondary hyperoxaluria. Primary hyperoxaluria constitutes a group of genetic disorders resulting in endogenous overproduction of oxalate, whereas secondary hyperoxaluria results from gastrointestinal disorders associated with fat malabsorption and increased absorption of dietary oxalate. In both conditions oxalate crystals can deposit in the kidney leading to renal failure. Since oxalate is primarily renally eliminated, it accumulates throughout the body in renal failure, a state termed oxalosis. Affected organs can include bones, joints, heart, eyes and skin. Since patients can present with renal failure and oxalosis before the underlying diagnosis of hyperoxaluria has been made, it is important to consider hyperoxaluria in patients who present with unexplained soft tissue crystal deposition. The best treatment of oxalosis is prevention. If patients present with advanced disease, treatment of oxalate arthritis consists of symptom management and control of the underlying disease process. PMID:23666469

  9. Resolution of a Challenge for Solvation Modeling: Calculation of Dicarboxylic Acid Dissociation Constants Using Mixed Discrete-Continuum Solvation Models

    SciTech Connect

    Marenich, Aleksandr; Ding, Wendu; Cramer, Christopher J.; Truhlar, Donald G.

    2012-06-07

    First and second dissociation constants (pKa values) of oxalic acid, malonic acid, and adipic acid were computed by using a number of theoretical protocols based on density functional theory and using both continuum solvation models and mixed discrete-continuum solvation models. We show that fully implicit solvation models (in which the entire solvent is represented by a dielectric continuum) fail badly for dicarboxylic acids with mean unsigned errors averaged over six pKa values) of 2.4-9.0 log units, depending on the particular implicit model used. The use of water-solute clusters and accounting for multiple conformations in solution significantly improve the performance of both generalized Born solvation models and models that solve the nonhomogeneous dielectric Poisson equation for bulk electrostatics. The four most successful models have mean unsigned errors of only 0.6-0.8 log units.

  10. Citrate and malonate increase microbial activity and alter microbial community composition in uncontaminated and diesel-contaminated soil microcosms

    NASA Astrophysics Data System (ADS)

    Martin, Belinda C.; George, Suman J.; Price, Charles A.; Shahsavari, Esmaeil; Ball, Andrew S.; Tibbett, Mark; Ryan, Megan H.

    2016-09-01

    Petroleum hydrocarbons (PHCs) are among the most prevalent sources of environmental contamination. It has been hypothesized that plant root exudation of low molecular weight organic acid anions (carboxylates) may aid degradation of PHCs by stimulating heterotrophic microbial activity. To test their potential implication for bioremediation, we applied two commonly exuded carboxylates (citrate and malonate) to uncontaminated and diesel-contaminated microcosms (10 000 mg kg-1; aged 40 days) and determined their impact on the microbial community and PHC degradation. Every 48 h for 18 days, soil received 5 µmol g-1 of (i) citrate, (ii) malonate, (iii) citrate + malonate or (iv) water. Microbial activity was measured daily as the flux of CO2. After 18 days, changes in the microbial community were assessed by a community-level physiological profile (CLPP) and 16S rRNA bacterial community profiles determined by denaturing gradient gel electrophoresis (DGGE). Saturated PHCs remaining in the soil were assessed by gas chromatography-mass spectrometry (GC-MS). Cumulative soil respiration increased 4- to 6-fold with the addition of carboxylates, while diesel contamination resulted in a small, but similar, increase across all carboxylate treatments. The addition of carboxylates resulted in distinct changes to the microbial community in both contaminated and uncontaminated soils but only a small increase in the biodegradation of saturated PHCs as measured by the n-C17 : pristane biomarker. We conclude that while the addition of citrate and malonate had little direct effect on the biodegradation of saturated hydrocarbons present in diesel, their effect on the microbial community leads us to suggest further studies using a variety of soils and organic acids, and linked to in situ studies of plants, to investigate the role of carboxylates in microbial community dynamics.

  11. 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.

  12. Proton and deuterium NMR experiments in zero field. [Perdeuterated p-demethoxybenzene, perdeuterated malonic acid, diethyl terephthalate-d4, nonadecane-2,2'-D2, sodium propionate-D2

    SciTech Connect

    Millar, J.M.

    1986-02-01

    High field solid-state NMR lineshapes suffer from inhomogeneous broadening since resonance frequencies are a function of molecular orientation. Time domain zero field NMR is a two-dimensional field-cycling technique which removes this broadening by probing the evolution of the spin system under zero applied field. The simplest version, the sudden transition experiment, induces zero field evolution by the sudden removal of the applied magnetic field. Theory and experimental results of this experiment and several variations using pulsed dc magnetic fuelds to initiate zero field evolution are presented. In particular, the pulsed indirect detection method allows detection of the zero field spectrum of one nuclear spin species via another (usually protons) by utilizing the level crossings which occur upon adiabatic demagnetization to zero field. Experimental examples of proton/deuteron systems are presented which demonstrate the method results in enhanced sensitivity relative to that obtained in sudden transition experiments performed directly on deuterium. High resolution /sup 2/H NQR spectra of a series of benzoic acid derivatives are obtained using the sudden transition and indirect detection methods. Librational oscillations in the water molecules of barium chlorate monohydrate are studied using proton and deuterium ZF experiments. 177 refs., 88 figs., 2 tabs.

  13. The hydratase activity of malonate semialdehyde decarboxylase: mechanistic and evolutionary implications.

    PubMed

    Poelarends, Gerrit J; Serrano, Hector; Johnson, William H; Hoffman, David W; Whitman, Christian P

    2004-12-01

    Malonate semialdehyde decarboxylase (MSAD) is a member of the tautomerase superfamily, a group of structurally homologous proteins that have a characteristic beta-alpha-beta-fold and a catalytic amino-terminal proline. In addition to its physiological decarboxylase activity, the conversion of malonate semialdehyde to acetaldehyde and carbon dioxide, the enzyme has now been found to display a promiscuous hydratase activity, converting 2-oxo-3-pentynoate to acetopyruvate, with a kcat/Km value of 6.0 x 102 M-1 s-1. Pro-1 and Arg-75 are critical for both activities, and the pKa of Pro-1 was determined to be approximately 9.2 by a direct 15N NMR titration. These observations implicate a decarboxylation mechanism in which Pro-1 polarizes the carbonyl oxygen of substrate by hydrogen bonding and/or an electrostatic interaction. Arg-75 may position the carboxylate group into a favorable orientation for decarboxylation. Both the hydratase activity and the pKa value of Pro-1 are shared with trans-3-chloroacrylic acid dehalogenase, another tautomerase superfamily member that precedes MSAD in a bacterial degradation pathway for trans-1,3-dichloropropene. Hence, MSAD and CaaD could have evolved by divergent evolution from a common ancestral protein, retaining the necessary catalytic components for the conjugate addition of water.

  14. 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.

  15. Regulation and evolution of malonate and propionate catabolism in proteobacteria.

    PubMed

    Suvorova, I A; Ravcheev, D A; Gelfand, M S

    2012-06-01

    Bacteria catabolize malonate via two pathways, encoded by the mdc and mat genes. In various bacteria, transcription of these genes is controlled by the GntR family transcription factors (TFs) MatR/MdcY and/or the LysR family transcription factor MdcR. Propionate is metabolized via the methylcitrate pathway, comprising enzymes encoded by the prp and acn genes. PrpR, the Fis family sigma 54-dependent transcription factor, is known to be a transcriptional activator of the prp genes. Here, we report a detailed comparative genomic analysis of malonate and propionate metabolism and its regulation in proteobacteria. We characterize genomic loci and gene regulation and identify binding motifs for four new TFs and also new regulon members, in particular, tripartite ATP-independent periplasmic (TRAP) transporters. We describe restructuring of the genomic loci and regulatory interactions during the evolution of proteobacteria.

  16. Free displacer and Ringbom displacer for a Malone refrigerator

    SciTech Connect

    Swift, G.W.; Brown, A.O.

    1994-05-01

    Malone refrigeration uses a liquid near its critical point (instead of the customary gas) as the working fluid in a Stirling, Brayton, or similar regenerative or recuperative cycle. Thus far, we have focused on the Stirling cycle, to avoid the difficult construction of the high-pressure-difference counterflow recuperator required for a Brayton machine. Our first Malone refrigerator used liquid propylene (C{sub 3}H{sub 6}) in a double-acting 4-cylinder Stirling configuration. First measurements with a free displacer used in a liquid working fluid are presented. The displacer was operated both in harmonic mode and in Ringbom mode, in liquid carbon dioxide. The results are in reasonable agreement with expectations.

  17. An oxalyl-CoA synthetase is important for oxalate metabolism in Saccharomyces cerevisiae

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  18. Deep catalytic oxidative desulfurization (ODS) of dibenzothiophene (DBT) with oxalate-based deep eutectic solvents (DESs).

    PubMed

    Lü, Hongying; Li, Pengcheng; Deng, Changliang; Ren, Wanzhong; Wang, Shunan; Liu, Pan; Zhang, Han

    2015-07-01

    An oxalate-based DES with a tetrabutyl ammonium chloride and oxalate acid molar ratio of 1/2 (TBO1 : 2) exhibited high activity in oxidative desulfurization (ODS) of dibenzothiophene (DBT) under mild reaction conditions. It is potentially a promising and highly environmentally friendly approach for desulfurization of fuels. PMID:26051675

  19. Durability of the Malone antegrade continence enema in pregnancy.

    PubMed

    Wren, Francis J; Reese, Carl T; Decter, Ross M

    2003-03-01

    The Malone antegrade continence enema (MACE) is a therapeutic option to treat chronic constipation and fecal incontinence in patients with neurogenic bowel. Previous reports have described the short-term success of this procedure, but no report has described the durability of the procedure during pregnancy. We present the case of a spinal cord injury patient who underwent an uncomplicated pregnancy after a MACE procedure with no stomal catheterization difficulties or leakage during or after the pregnancy.

  20. Acute environmental toxicity and persistence of DEM, a chemical agent simulant: Diethyl malonate. [Diethyl malonate

    SciTech Connect

    Cataldo, D.A.; Ligotke, M.W.; Harvey, S.D.; Fellows, R.J.; Li, Shu-mei W.; Van Voris, P.; Wentsel, R.S.

    1990-05-01

    The purpose of the following chemical simulant studies is to assess the potential acute environmental effects and persistence of diethyl malonate (DEM). Deposition velocities for DEM to soil surfaces ranged from 0.04 to 0.2 cm/sec. For foliar surfaces, deposition velocities ranged from 0.0002 cm/sec at low air concentrations to 0.05 cm/sec for high dose levels. The residence times or half-lives of DEM deposited to soils was 2 h for the fast component and 5 to 16 h for the residual material. DEM deposited to foliar surfaces also exhibited biphasic depuration. The half-life of the short residence time component ranged from 1 to 3 h, while the longer time component had half-times of 16 to 242 h. Volatilization and other depuration mechanisms reduce surface contaminant levels in both soils and foliage to less than 1% of initial dose within 96 h. DEM is not phytotoxic at foliar mass loading levels of less than 10 {mu}m/cm{sup 2}. However, severe damage is evident at mass loading levels in excess of 17 {mu}g/cm{sup 2}. Tall fescue and sagebrush were more affected than was short-needle pine, however, mass loading levels were markedly different. Regrowth of tall fescue indicated that the effects of DEM are residual, and growth rates are affected only at higher mass loadings through the second harvest. Results from in vitro testing of DEM indicated concentrations below 500 {mu}g/g dry soil generally did not negatively impact soil microbial activity. Short-term effects of DEM were more profound on soil dehydrogenase activity than on soil phosphatase activity. No enzyme inhibition or enhancement was observed after 28 days in incubation. Results of the earthworm bioassay indicate survival to be 86 and 66% at soil doses of 107 and 204 {mu}g DEM/cm{sup 2}, respectively. At higher dose level, activity or mobility was judged to be affected in over 50% of the individuals. 21 refs., 10 figs., 15 tabs.

  1. Reflectance spectroscopy of oxalate minerals and relevance to Solar System carbon inventories

    NASA Astrophysics Data System (ADS)

    Applin, Daniel M.; Izawa, Matthew R. M.; Cloutis, Edward A.

    2016-11-01

    The diversity of oxalate formation mechanisms suggests that significant concentrations of oxalic acid and oxalate minerals could be widely distributed in the Solar System. We have carried out a systematic study of the reflectance spectra of oxalate minerals and oxalic acid, covering the 0.2-16 μm wavelength region. Our analyses show that oxalates exhibit unique spectral features that enable discrimination between oxalate phases and from other commonly occurring compounds, including carbonates, in all regions of the spectrum except for the visible. Using these spectral data, we consider the possible contribution of oxalate minerals to previously observed reflectance spectra of many objects throughout the Solar System, including satellites, comets, and asteroids. We find that polycarboxylic acid dimers and their salts may explain the reflectance spectra of many carbonaceous asteroids in the 3 μm spectral region. We suggest surface concentration of these compounds may be a type of space weathering from the photochemical and oxidative decomposition of the organic macromolecular material found in carbonaceous chondrites. The stability and ubiquity of these minerals on Earth, in extraterrestrial materials, and in association with biological processes make them useful for many applications in Earth and planetary sciences.

  2. Plutonium oxalate precipitation for trace elemental determination in plutonium materials

    DOE PAGES

    Xu, Ning; Gallimore, David; Lujan, Elmer; Garduno, Katherine; Walker, Laurie; Taylor, Fiona; Thompson, Pam; Tandon, Lav

    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.

  3. Antioxidant properties of Krebs cycle intermediates against malonate pro-oxidant activity in vitro: a comparative study using the colorimetric method and HPLC analysis to determine malondialdehyde in rat brain homogenates.

    PubMed

    Puntel, Robson Luiz; Roos, Daniel Henrique; Grotto, Denise; Garcia, Solange C; Nogueira, Cristina Wayne; Rocha, Joao Batista Teixeira

    2007-06-13

    A variety of Krebs cycle intermediaries has been shown to possess antioxidant properties in different in vivo and in vitro systems. Here we examined whether citrate, succinate, malate, oxaloacetate, fumarate and alpha-ketoglutarate could modulate malonate-induced thiobarbituric acid-reactive species (TBARS) production in rat brain homogenate. The mechanisms involved in their antioxidant activity were also determined using two analytical methods: 1) a popular spectrophotometric method (Ohkawa, H., Ohishi, N., Yagi, K., 1979. Assay for lipid peroxides in animal tissues by thiobarbituric acid reaction. Analytical Biochemistry 95, 351-358.) and a high performance liquid chromatographic (HPLC) procedure (Grotto, D., Santa Maria, L. D., Boeira, S., Valentini, J., Charão, M. F., Moro, A. M., Nascimento, P. C., Pomblum, V. J., Garcia, S. C., 2006. Rapid quantification of malondialdehyde in plasma by high performance liquid chromatography-visible detection. Journal of Pharmaceutical and Biomedical Analysis 43, 619-624.). Citrate, malate, and oxaloacetate reduced both basal and malonate-induced TBARS production. Their effects were not changed by pre-treatment of rat brain homogenates at 100 degrees C for 10 min. alpha-Ketoglutarate increased basal TBARS without changing malonate-induced TBARS production in fresh and heat-treated homogenates. Succinate reduced basal--without altering malonate-induced TBARS production. Its antioxidant activity was abolished by KCN or heat treatment. Fumarate reduced malonate-induced TBARS production in fresh homogenates; however, its effect was completely abolished by heat treatment. There were minimal differences among the studied methods. Citrate, oxaloacetate, malate, alpha-ketoglutarate and malonate showed iron-chelating activity. We suggest that antioxidant properties of citrate, malate and oxaloacetate were due to their ability to cancel iron redox activity by forming inactive complexes, whereas alpha-ketoglutarate and malonate pro

  4. Oxalate Mass Balance During Chemical Cleaning in Tank 5F

    SciTech Connect

    Poirier, M.; Fink, S.

    2011-07-08

    The Savannah River Site (SRS) is preparing Tank 5F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning to determine whether the tank is ready for closure. SRS personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of the chemical cleaning process. Analysis of the anions showed the measured oxalate removed from Tank 5F to be approximately 50% of the amount added in the oxalic acid. To close the oxalate mass balance, the author collected solid samples, leached them with nitric acid, and measured the concentration of cations and anions in the leachate.

  5. The dissolution of quartz in dilute aqueous solutions of organic acids at 25 degree C

    SciTech Connect

    Bennett, P.C.; Melcer, M.E.; Siegel, D.I.; Hassett, J.P. )

    1988-06-01

    The dissolution of quartz in dilute aqueous solutions of organic acids at 25{degree}C and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 {mu}mole/Kg compared to 50 {mu}mole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH. The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

  6. The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

    NASA Astrophysics Data System (ADS)

    Bennett, P. C.; Melcer, M. E.; Siegel, D. I.; Hassett, J. P.

    1988-06-01

    The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH. The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

  7. Protection of Metal Artifacts with the Formation of Metal-Oxalates Complexes by Beauveria bassiana.

    PubMed

    Joseph, Edith; Cario, Sylvie; Simon, Anaële; Wörle, Marie; Mazzeo, Rocco; Junier, Pilar; Job, Daniel

    2011-01-01

    Several fungi present high tolerance to toxic metals and some are able to transform metals into metal-oxalate complexes. In this study, the ability of Beauveria bassiana to produce copper oxalates was evaluated. Growth performance was tested on various copper-containing media. B. bassiana proved highly resistant to copper, tolerating concentrations of up to 20 g L(-1), and precipitating copper oxalates on all media tested. Chromatographic analyses showed that this species produced oxalic acid as sole metal chelator. The production of metal-oxalates can be used in the restoration and conservation of archeological and modern metal artifacts. The production of copper oxalates was confirmed directly using metallic pieces (both archeological and modern). The conversion of corrosion products into copper oxalates was demonstrated as well. In order to assess whether the capability of B. bassiana to produce metal-oxalates could be applied to other metals, iron and silver were tested as well. Iron appears to be directly sequestered in the wall of the fungal hyphae forming oxalates. However, the formation of a homogeneous layer on the object is not yet optimal. On silver, a co-precipitation of copper and silver oxalates occurred. As this greenish patina would not be acceptable on silver objects, silver reduction was explored as a tarnishing remediation. First experiments showed the transformation of silver nitrate into nanoparticles of elemental silver by an unknown extracellular mechanism. The production of copper oxalates is immediately applicable for the conservation of copper-based artifacts. For iron and silver this is not yet the case. However, the vast ability of B. bassiana to transform toxic metals using different immobilization mechanisms seems to offer considerable possibilities for industrial applications, such as the bioremediation of contaminated soils or the green synthesis of chemicals. PMID:22291684

  8. Study on Dicarboxylic Acids in Aerosol Samples with Capillary Electrophoresis

    PubMed Central

    Adler, Heidi; Sirén, Heli

    2014-01-01

    The research was performed to study the simultaneous detection of a homologous series of α, ω-dicarboxylic acids (C2–C10), oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, and sebacic acids, with capillary electrophoresis using indirect UV detection. Good separation efficiency in 2,6-pyridinedicarboxylic acid as background electrolyte modified with myristyl trimethyl ammonium bromide was obtained. The dicarboxylic acids were ionised and separated within five minutes. For the study, authentic samples were collected onto dry cellulose membrane filters of a cascade impactor (12 stages) from outdoor spring aerosols in an urban area. Hot water and ultrasonication extraction methods were used to isolate the acids from membrane filters. Due to the low concentrations of acids in the aerosols, the extracts were concentrated with solid-phase extraction (SPE) before determination. The enrichment of the carboxylic acids was between 86 and 134% with sample pretreatment followed by 100-time increase by preparation of the sample to 50 μL. Inaccuracy was optimised for all the sample processing steps. The aerosols contained dicarboxylic acids C2–C10. Then, mostly they contained C2, C5, and C10. Only one sample contained succinic acid. In the study, the concentrations of the acids in aerosols were lower than 10 ng/m3. PMID:24729915

  9. Renal histopathology and crystal deposits in patients with small bowel resection and calcium oxalate stone disease.

    PubMed

    Evan, Andrew P; Lingeman, James E; Worcester, Elaine M; Bledsoe, Sharon B; Sommer, Andre J; Williams, James C; Krambeck, Amy E; Philips, Carrie L; Coe, Fredric L

    2010-08-01

    We present here the anatomy and histopathology of kidneys from 11 patients with renal stones following small bowel resection, including 10 with Crohn's disease and 1 resection in infancy for unknown cause. They presented predominantly with calcium oxalate stones. Risks of formation included hyperoxaluria (urine oxalate excretion greater than 45 mg per day) in half of the cases, and acidic urine of reduced volume. As was found with ileostomy and obesity bypass, inner medullary collecting ducts (IMCDs) contained crystal deposits associated with cell injury, interstitial inflammation, and papillary deformity. Cortical changes included modest glomerular sclerosis, tubular atrophy, and interstitial fibrosis. Randall's plaque (interstitial papillary apatite) was abundant, with calcium oxalate stone overgrowth similar to that seen in ileostomy, idiopathic calcium oxalate stone formers, and primary hyperparathyroidism. Abundant plaque was compatible with the low urine volume and pH. The IMCD deposits all contained apatite, with calcium oxalate present in three cases, similar to findings in patients with obesity bypass but not an ileostomy. The mechanisms for calcium oxalate stone formation in IMCDs include elevated urine and presumably tubule fluid calcium oxalate supersaturation, but a low calcium to oxalate ratio. However, the mechanisms for the presence of IMCD apatite remain unknown.

  10. [Compositions of organic acids in PM10 emission sources in Xiamen urban atmosphere].

    PubMed

    Yang, Bing-Yu; Huang, Xing-Xing; Zheng, An; Liu, Bi-Lian; Wu, Shui-Ping

    2013-01-01

    The possible organic acid emission sources in PM10 in Xiamen urban atmosphere such as cooking, biomass burning, vehicle exhaust and soil/dust were obtained using a re-suspension test chamber. A total of 15 organic acids including dicarboxylic acids, fatty acids and aromatic acids were determined using GC/MS after derivatization with BF3/n-butanol. The results showed that the highest total concentration of 15 organic acids (53%) was found in cooking emission and the average concentration of the sum of linoleic acid and oleic acid was 24% +/- 14%. However, oxalic acid was the most abundant species followed by phthalic acid in gasoline vehicle exhaust. The ratios of adipic to azelaic acid in gasoline combustion emissions were significantly higher than those in other emission sources, which can be used to qualitatively differentiate anthropogenic and biological source of dicarboxylic acids in atmospheric samples. The ratios of malonic to succinic acid in source emissions (except gasoline generator emissions) were lower (0.07-0.44) than ambient PM10 samples (0.61-3.93), which can be used to qualitatively differentiate the primary source and the secondary source of dicarboxylic acids in urban PM10.

  11. Separation and recovery of plutonium from oxalate supernatant using CMPO

    SciTech Connect

    Mathur, J.N.; Murali, M.S.; Rizvi, G.H.; Iyer, R.H.; Michael, K.M.; Kapoor, S.C.; Dhumwad, R.K.; Badheka, L.P.; Banerji, A. )

    1994-08-01

    A simple and efficient procedure has been developed to quantitatively recover Pu from oxalate supernatant using a mixture of octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and TBP in dodecane. Pu(IV) in the range of 6.9 to 34.6 mg/l was quantitatively extracted into 0.2M CMPO + 1.2 M TBP in dodecane from an aqueous solution containing 3.0 M HNO[sub 3] and 0.1 M H[sub 2]C[sub 2]O[sub 4]. At such low concentrations of Pu, the distribution ratio (D) did not change but the increase in oxalic acid concentration drastically reduced these values. The variation in HNO[sub 3] concentration at a fixed concentration of 0.2 M CMPO + U 1.2 M TBP has shown a dramatic increase in the D values, being 0.3 at 1.0 M and >10[sup 4] at 7.5 M. The extraction was almost quantitative even at the aqueous-to-organic ratio of 10:1. Plutonium could be quantitatively recovered by (i) stripping with 0.5 M acetic acid and (ii) coprecipitating it directly from the organic phase with 0.3 M oxalic acid + 0.3 M calcium nitrate + sodium nitrite. [approximately] 92% of the Pu was found in the precipitate and [approximately] 7% in the supernant. Using this procedure, Pu in a concentrated form ([approximately] 50 times) could be recovered from the oxalate supernatant solutions without recourse to the destruction of oxalate ion. 19 refs., 5 figs., 5 tabs.

  12. Rainwater monocarboxylic and dicarboxylic acid concentrations in southeastern North Carolina, USA, as a function of air-mass back-trajectory

    NASA Astrophysics Data System (ADS)

    Brooks Avery, G.; Kieber, Robert J.; Witt, Melanie; Willey, Joan D.

    Eight organic acids were measured in 111 rain events occurring between September 1996 and May 1998 in Wilmington, North Carolina. Formic and acetic acids were the most abundant comprising approximately 75% of the total molar quantity of organic acids. The annual volume-weighted concentrations of organic acids in order of decreasing abundance in rainwater was formic (9.9 μM), acetic (7.3 μM), oxalic (1.8 μM), lactic (1.3 μM), succinic (1.0 μM), malonic (0.7 μM), pyruvic (0.3 μM), and maleic (0.1 μM), with methanesulfonic and glyoxylic acids usually below their detection limit. Growing season back-trajectory data provided strong evidence that terrestrial organic acid sources dominated over marine sources. Air mass back-trajectory analysis indicated that during the growing season air mass origin had a consistent impact on concentrations of rainwater organic acids. Rain with continental back-trajectories coming from the west had the highest concentrations of organic acids while two predominately marine back-trajectories had the lowest concentrations. Concentrations of organic acids in non-growing season rain did not display a consistent pattern indicating variability in sources. Seasonality of individual organic acids for specific back-trajectories was most pronounced in terrestrial back-trajectories and least in the marine back-trajectories indicating that seasonality in rainwater organic acid concentrations is driven by variations in terrestrial sources. Formic to acetic acid ratios (F:A), previously an indicator of terrestrial versus marine sources of these organic acids, were similar for all back-trajectories reflecting anthropogenic impacts on F:A locally and regionally. The ratios of malonic to succinic acids (M:S), also an indicator of sources for these acids, indicated direct anthropogenic sources for terrestrial back-trajectories and secondary processes for marine back-trajectories.

  13. 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.

  14. REINVESTIGATING THE PROCESS IMPACTS FROM OXALIC ACIDHIGH LEVEL WASTE TANK CLEANING

    SciTech Connect

    Ketusky, E

    2008-01-22

    The impacts and acceptability of using oxalic acid to clean the Savannah River Site, High Level Waste Tanks 1-8, were re-investigated using a two-phased approach. For the first phase, using a representative Tank 1-8 sludge, the chemical equilibrium based software, OLI ESP{copyright} and Savannah River Site laboratory test results were used to develop a chemically speciated material balance and a general oxalate mass balance. Using 8 wt% oxalic acid with a 100% molar excess, for every 1 kg of sludge solid that was dissolved, about 3.4 kg of resultant solids would form for eventual vitrification, while about 0.6 kg of soluble oxalate would precipitate in the evaporator system, and form a salt heel. Using available analyses, a list of potential safety and process impacts were developed, screened, and evaluated for acceptability. The results showed that the use of oxalic acid had two distinct types of impacts, those which were safety based and required potential upgrades or additional studies. Assuming such were performed and adequate, no further actions were required. The second type of impacts were also acceptable, but were long-term, and as such, would need to be managed. These impacts were directly caused by the solubility characteristics of oxalate in a concentrated sodium solution and, occurred after pH restoration. Since oxalate destruction methods are commonly available, their use should be considered. Using an oxalate destruction method could enable the benefits of oxalic to applied, while eliminating the long-term impacts that must be managed, and hence should be considered.

  15. Formation of water-soluble dicarboxylic acids, oxoacids and a-dicarbonyls by ozone oxidation of isoprene

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Tachibana, E.; Sakamoto, Y.; Hirokawa, J.

    2014-12-01

    Water-soluble dicarboxylic acids such as oxalic acid (C2) are the dominant organic compound class in atmospheric aerosols. They can act as cloud condensation nuclei and affect on the Earth climate. Diacids can be primary emitted from fossil fuel combustion and biomass burning and secondarily produced by photochemical oxidations of biogenic and anthropogenic hydrocarbons. However, their sources and formation processes are still not well understood. Recently model and observation studies suggested the importance of isoprene as a precursor of oxalic acid. Isoprene is the most abundant BVOC emitted from terrestrial plants and can serve as important precursors of diacids. We conducted a laboratory oxidation of isoprene (2.0 ppm) with ozone (4.3 ppm) in a Teflon bag for 10 to 480 min. The formed particles were collected with quartz fiber filters and analyzed for diacids, oxoacids and a-dicarbonyls employing water extraction and butyl ester derivatization and using GC and GC/MS techniques. Here, we report the analytical results to better understand the formation process of diacids and related compounds from isoprene. We detected homologous series of saturated diacids (C2-C6), unsaturated diacids (maleic and methylmaleic acids), w-oxocarboxylic acids (C2-C9), pyruvic acid, glyoxal and methylglyoxal. We found that oxalic acid (3000-9700 ngm-3) is the most abundant diacid followed by succinic (C4) or malonic (C3) acid. Their concentrations increased with reaction time showing a maximum in 4 hours. Interestingly, C3/C4 ratios increased with time. The second most abundant species after oxalic acid was generally methylglyoxal (3600-9600 ngm-3), except for the 30 min. sample where methylglyoxal was more abundant than oxalic acid. Glyoxylic acid (wC2) was found as the most abundant oxoacid (1600-3800 ngm-3) followed by wC3 and wC4. Although the concentrations of diacids and related compounds are 1-2 orders magnitude higher than those reported in ambient aerosols, this study

  16. 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

  17. 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.

  18. Dissolution mechanisms of goethite in the presence of siderophores and organic acids

    NASA Astrophysics Data System (ADS)

    Reichard, P. U.; Kretzschmar, R.; Kraemer, S. M.

    2007-12-01

    In dynamic natural systems such as soils and surface waters, transient biogeochemical processes can induce strong chemical non-steady-state conditions. In this paper, we investigate the effects of non-steady-state conditions on ligand-controlled iron oxide dissolution. The rates of goethite dissolution at pH 6 in the presence of low molecular weight organic acids (oxalate, citrate or malonate) were observed. Non-steady-state conditions were induced by rapid additions of fungal, bacterial or plant siderophores. In the presence of the low molecular weight organic acids, dissolved iron concentrations are below detection limit as predicted by equilibrium solubility calculations. The rapid addition of the siderophores triggered reproducible, fast dissolution of kinetically labile iron from the iron oxide surface. The same effect was observed upon rapid additions of high citrate concentrations to goethite-oxalate suspensions. The concentration of the labile iron pool at the mineral surface was a function of the surface concentration of the low molecular weight organic acids and of the reaction time before addition of the siderophores. Isotopic exchange with 59Fe independently confirmed the existence of the labile iron pool before addition of the siderophore. A dissolution mechanism was elucidated that is consistent with these observations and with accepted models of ligand-controlled dissolution. We conclude that the fast dissolution reaction observed here is an important process in biological iron acquisition and that it is based on a general geochemical mechanism.

  19. Atmospheric dry plus wet deposition and wet-only deposition of dicarboxylic acids and inorganic compounds in a coastal suburban environment

    NASA Astrophysics Data System (ADS)

    Tsai, Ying I.; Kuo, Su-Ching; Young, Li-Hao; Hsieh, Li-Ying; Chen, Pei-Ti

    2014-06-01

    This study investigated the chemical properties and composition sources of dicarboxylic organic acids and inorganic salts in dry plus wet deposition (DWD) and wet-only deposition at a coastal suburban area in southern Taiwan in 2008. DWD is the accumulation of dry deposition and wet deposition from the beginning of each new rain event, while wet-only deposition is the wet deposition from the beginning of each new rain event only. A total of 60 samples were collected during the period of study. The wet-only deposition samples were slightly more acidic (pH 5.01-5.50) than the DWD samples (pH 5.51-6.00). The total volume-weighted mean (VWM) equivalent ionic concentration of 784.3 ± 431.1 μeq L-1 in DWD was higher than that of 682.2 ± 392.4 μeq L-1 in wet-only deposition. In both types of deposition the major cation species were Ca2+, Na+ and NH4+, and the major anion species were HCO3-, Cl- and non-sea salt (nss) nss-SO42-. Total dicarboxylic acids contributed only 0.60% and 0.45% of the total ionic equivalent concentration in DWD and wet-only deposition, respectively, and oxalic and malonic acids were the major dicarboxylic acid species. DWD to wet-only deposition species concentration ratios (DWD/W ratios) were always higher than 1.0. DWD contained more water-soluble inorganic salts and dicarboxylic acids than wet-only deposition, with DWD/W ratios of the dust-bound species K+, Mg2+ and Ca2+ as large as 1.6-1.8 and those from photochemical species nss-SO42- and NH4+ of 1.36 and 1.29, respectively. These ratios show that the dry deposition flux of dust is greater than that of photochemical particles. In addition, the 1.81 ratio for oxalic acid shows that oxalic acid is easier to remove from the atmosphere via dry deposition than malonic and succinic acids. Probable deposition composition sources for both DWD and wet-only deposition, investigated using principal component analysis, were marine spray, photochemical inorganic products, and terrestrial origin and

  20. Raman spectra of oxalates in lichen encrustations on Renaissance frescoes

    NASA Astrophysics Data System (ADS)

    Edwards, H. G. M.; Farwell, D. W.; Seaward, M. R. D.

    The vibrational Raman spectra of lichen encrustations on biodeteriorated Renaissance frescoes have been recorded using a laser Raman microprobe. The major chemical species identified in the encrustations is calcium oxalate. Other vibrational features in the Raman spectra have been assigned to fragments of the substratum incorporated from the biodeterioration process and to organic by-products of lichen metabolism such as erythrin, lecanoric acid and meso-erythritol.

  1. 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

  2. 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

  3. Oxalate: from the environment to kidney stones.

    PubMed

    Brzica, Hrvoje; Breljak, Davorka; Burckhardt, Birgitta C; Burckhardt, Gerhard; Sabolić, Ivan

    2013-12-01

    Oxalate urolithiasis (nephrolithiasis) is the most frequent type of kidney stone disease. Epidemiological research has shown that urolithiasis is approximately twice as common in men as in women, but the underlying mechanism of this sex-related prevalence is unclear. Oxalate in the organism partially originate from food (exogenous oxalate) and largely as a metabolic end-product from numerous precursors generated mainly in the liver (endogenous oxalate). Oxalate concentrations in plasma and urine can be modified by various foodstuffs, which can interact in positively or negatively by affecting oxalate absorption, excretion, and/or its metabolic pathways. Oxalate is mostly removed from blood by kidneys and partially via bile and intestinal excretion. In the kidneys, after reaching certain conditions, such as high tubular concentration and damaged integrity of the tubule epithelium, oxalate can precipitate and initiate the formation of stones. Recent studies have indicated the importance of the SoLute Carrier 26 (SLC26) family of membrane transporters for handling oxalate. Two members of this family [Sulfate Anion Transporter 1 (SAT-1; SLC26A1) and Chloride/Formate EXchanger (CFEX; SLC26A6)] may contribute to oxalate transport in the intestine, liver, and kidneys. Malfunction or absence of SAT-1 or CFEX has been associated with hyperoxaluria and urolithiasis. However, numerous questions regarding their roles in oxalate transport in the respective organs and male-prevalent urolithiasis, as well as the role of sex hormones in the expression of these transporters at the level of mRNA and protein, still remain to be answered. PMID:24384768

  4. Seasonal and longitudinal distributions of atmospheric water-soluble dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls over the North Pacific

    NASA Astrophysics Data System (ADS)

    Bikkina, Srinivas; Kawamura, Kimitaka; Imanishi, Katsuya; Boreddy, S. K. R.; Nojiri, Yukihiro

    2015-05-01

    In order to assess the seasonal variability of atmospheric abundances of dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls over the North Pacific and Sea of Japan, aerosol samples were collected along the longitudinal transacts during six cruises between Canada and Japan. The back trajectory analyses indicate that aerosol samples collected in winter and spring are influenced by the East Asian outflow, whereas summer and fall samples are associated with the pristine maritime air masses. Molecular distributions of water-soluble organics in winter and spring samples show the predominance of oxalic acid (C2) followed by succinic (C4) and malonic acids (C3). In contrast, summer and fall marine aerosols are characterized by the predominance of C3 over C4. Concentrations of dicarboxylic acids were higher over the Sea of Japan than the North Pacific. With a lack of continental outflow, higher concentrations during early summer are ascribed to atmospheric oxidation of organic precursors associated with high biological activity in the North Pacific. This interpretation is further supported by the high abundances of azelaic acid, which is a photochemical oxidation product of biogenic unsaturated fatty acids, over the Bering Sea in early summer when surface waters are characterized by high biological productivity. We found higher ratios of oxalic acid to pyruvic and glyoxylic acids (C2/Pyr and C2/ωC2) and glyoxal and methylglyoxal (C2/Gly and C2/MeGly) in summer and fall than in winter and spring, suggesting a production of C2 from the aqueous-phase oxidation of oceanic isoprene. In this study, dicarboxylic acids account for 0.7-38% of water-soluble organic carbon.

  5. Oxalobacter sp. reduces urinary oxalate excretion by promoting enteric oxalate secretion.

    PubMed

    Hatch, M; Cornelius, J; Allison, M; Sidhu, H; Peck, A; Freel, R W

    2006-02-01

    The primary goal of this study was to test the hypothesis that Oxalobacter colonization alters colonic oxalate transport thereby reducing urinary oxalate excretion. In addition, we examined the effects of intraluminal calcium on Oxalobacter colonization and tested the hypothesis that endogenously derived colonic oxalate could be degraded by lyophilized Oxalobacter enzymes targeted to this segment of the alimentary tract. Oxalate fluxes were measured across short-circuited, in vitro preparations of proximal and distal colon removed from Sprague-Dawley rats and placed in Ussing chambers. For these studies, rats were colonized with Oxalobacter either artificially or naturally, and urinary oxalate, creatinine and calcium excretions were determined. Colonized rats placed on various dietary treatment regimens were used to evaluate the impact of calcium on Oxalobacter colonization and whether exogenous or endogenous oxalate influenced colonization. Hyperoxaluric rats with some degree of renal insufficiency were also used to determine the effects of administering encapsulated Oxalobacter lysate on colonic oxalate transport and urinary oxalate excretion. We conclude that in addition to its intraluminal oxalate-degrading capacity, Oxalobacter interacts physiologically with colonic mucosa by inducing enteric oxalate secretion/excretion leading to reduced urinary excretion. Whether Oxalobacter, or products of Oxalobacter, can therapeutically reduce urinary oxalate excretion and influence stone disease warrants further investigation in long-term studies in various patient populations. PMID:16518326

  6. Association analysis for oxalate concentration in spinach

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  7. Engineering calcium oxalate crystal formation in Arabidopsis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  8. Dicarboxylic acids, oxoacids, benzoic acid, α-dicarbonyls, WSOC, OC, and ions in spring aerosols from Okinawa Island in the western North Pacific Rim: size distributions and formation processes

    NASA Astrophysics Data System (ADS)

    Deshmukh, D. K.; Kawamura, K.; Lazaar, M.; Kunwar, B.; Boreddy, S. K. R.

    2015-09-01

    Size-segregated aerosols (9-stages from < 0.43 to > 11.3 μm in diameter) were collected at Cape Hedo, Okinawa in spring 2008 and analyzed for water-soluble diacids (C2-C12), ω-oxoacids (ωC2-ωC9), pyruvic acid, benzoic acid and α-dicarbonyls (C2-C3) as well as water-soluble organic carbon (WSOC), organic carbon (OC) and major ions. In all the size-segregated aerosols, oxalic acid (C2) was found as the most abundant species followed by malonic and succinic acids whereas glyoxylic acid (ωC2) was the dominant oxoacid and glyoxal (Gly) was more abundant than methylglyoxal. Diacids (C2-C5), ωC2 and Gly as well as WSOC and OC peaked at 0.65-1.1 μm in fine mode whereas azelaic (C9) and 9-oxononanoic (ωC9) acids peaked at 3.3-4.7 μm in coarse mode. Sulfate and ammonium are enriched in fine mode whereas sodium and chloride are in coarse mode. These results imply that water-soluble species in the marine aerosols could act as cloud condensation nuclei (CCN) to develop the cloud cover over the western North Pacific Rim. The organic species are likely produced by a combination of gas-phase photooxidation, and aerosol-phase or in-cloud processing during long-range transport. The coarse mode peaks of malonic and succinic acids were obtained in the samples with marine air masses, suggesting that they may be associated with the reaction on sea salt particles. Bimodal size distributions of longer-chain diacid (C9) and oxoacid (ωC9) with a major peak in the coarse mode suggest their production by photooxidation of biogenic unsaturated fatty acids via heterogeneous reactions on sea salt particles.

  9. Environmental persistence and toxicity of dimethyl malonate and methyl salicylate

    SciTech Connect

    Fellows, R.J.; Harvey, S.D.; Ligotke, M.W.; Cataldo, D.A.; Li, S.W.; Van Voris, P. ); Wentsel, R.S. )

    1991-03-01

    To determine the potential environmental persistence and toxic effects of agent simulants Diethyl Malonate (DEM) and Methyl Salicylate (MS), plants, soils, earthworms, and oil microbial populations were exposed to projected aerosolized simulant concentrations of {approximately}100 (low) and {approximately}1000 (high) mg/m{sup 3}. Both simulants exhibited biphasic residence times on foliar and soil surfaces following aerosol exposure. Half-times of DEM on soil and foliar surfaces were 1 to 3 h and 5 to 22 H, respectively, and 2 to 2 h and 5 to 31 h for the MS, respectively. Persistence was longer on the foliar surfaces than that of the soils. Both simulants proved phytotoxic to vegetation with a lower threshold of 1 to 2 {mu}m/cm{sup 2} for the MS versus that of 10 {mu}g/cm{sup 2} for the DEM. However, neither significantly affected chloroplast electron transport in vitro at concentrations of up to 100 {mu}g/mL. Results from in vitro testing of DEM indicated concentrations below 500 {mu}g/g dry soil generally did not adversely impact soil microbial activity, while the theshold was 100 {mu}g/g dry soil for MS. Earthworm bioassays indicated survival rates of 66% at soil doses of 204 {mu}g DEM/cm{sup 2} soil and 86% at soil doses of 331 {mu}g MS/cm{sup 2}. 8 refs., 1 fig., 8 tabs.

  10. Aqueous Phase Photo-Oxidation of Succinic Acid: Changes in Hygroscopic Properties and Reaction Products

    NASA Astrophysics Data System (ADS)

    Hudson, P. K.; Ninokawa, A.; Hofstra, J.; de Lijser, P.

    2013-12-01

    Atmospheric aerosol particles have been identified as important factors in understanding climate change. The extent to which aerosols affect climate is determined, in part, by hygroscopic properties which can change as a result of atmospheric processing. Dicarboxylic acids, components of atmospheric aerosol, have a wide range of hygroscopic properties and can undergo oxidation and photolysis reactions in the atmosphere. In this study, the hygroscopic properties of succinic acid aerosol, a non-hygroscopic four carbon dicarboxylic acid, were measured with a humidified tandem differential mobility analyzer (HTDMA) and compared to reaction products resulting from the aqueous phase photo-oxidation reaction of hydrogen peroxide and succinic acid. Reaction products were determined and quantified using gas chromatography-flame ionization detection (GC-FID) and GC-mass spectrometry (GC-MS) as a function of hydrogen peroxide:succinic acid concentration ratio and photolysis time. Although reaction products include larger non-hygroscopic dicarboxylic acids (e.g. adipic acid) and smaller hygroscopic dicarboxylic acids (e.g. malonic and oxalic acids), comparison of hygroscopic growth curves to Zdanovskii-Stokes-Robinson (ZSR) predictions suggests that the hygroscopic properties of many of the product mixtures are largely independent of the hygroscopicity of the individual components. This study provides a framework for future investigations to fully understand and predict the role of chemical reactions in altering atmospheric conditions that affect climate.

  11. pH dependency of sclerotial development and pathogenicity revealed by using genetically defined oxalate-minus mutants of Sclerotinia sclerotiorum.

    PubMed

    Xu, Liangsheng; Xiang, Meichun; White, David; Chen, Weidong

    2015-08-01

    The devastating plant pathogen Sclerotinia sclerotiorum produces copious (up to 50 mM) amounts of oxalic acid, which, for over a quarter century, has been claimed as the pathogenicity determinant based on UV-induced mutants that concomitantly lost oxalate production and pathogenicity. Such a claim was made without fulfilling the molecular Koch's postulates because the UV mutants are genetically undefined and harbour a developmental defect in sclerotial production. Here, we generated oxalate-minus mutants of S. sclerotiorum using two independent mutagenesis techniques, and tested the resulting mutants for growth at different pHs and for pathogenicity on four host plants. The oxalate-minus mutants accumulated fumaric acid, produced functional sclerotia and have reduced ability to acidify the environment. The oxalate-minus mutants retained pathogenicity on plants, but their virulence varied depending on the pH and buffering capacity of host tissue. Acidifying the host tissue enhanced virulence of the oxalate-minus mutants, whereas supplementing with oxalate did not. These results suggest that it is low pH, not oxalic acid itself, that establishes the optimum conditions for growth, reproduction, pathogenicity and virulence expression of S. sclerotiorum. Exonerating oxalic acid as the primary pathogenicity determinant will stimulate research into identifying additional candidates as pathogenicity factors towards better understanding and managing Sclerotinia diseases. PMID:25720941

  12. Effect of Oxalate on the Recycle of Neptunium Filtrate Solution by Anion Exchange

    SciTech Connect

    Kyser, E

    2004-11-18

    A series of laboratory column runs has been performed that demonstrates the recovery of neptunium (Np) containing up to 0.05 M oxalate. Np losses were generally less than one percent to the raffinate for feed solutions that contained 2 to 10 g Np/L. Up to 16 percent Np losses were observed with lower Np feed concentrations, but those losses were attributed to the shortened residence times rather than the higher oxalate to Np ratios. Losses in the plant are expected to be significantly less due to the lower cross-section flowrate possible with existing plant pumps. Elimination of the permanganate treatment of filtrates appears to be reasonable since the amount of Np in those filtrates does not appear to be practical to recover. Combination of untreated filtrates with other actinide rich solutions is not advisable as precipitation problems are likely. If untreated filtrates are kept segregated from other actinide rich streams, the recovery of the remaining Np is probably still possible, but could be limited due to the excessively high oxalate to Np ratio. The persistence of hydrazine/hydrazoic acid in filtrate solutions dictates that the nitrite treatment be retained to eliminate those species from the filtrates prior to transfer to the canyon. Elimination of the permanganate treatment of precipitator flushes and recovery by anion exchange does not appear to be limited by the oxalate effect on anion exchange. Np from solutions with higher oxalate to Np molar ratios than expected in precipitator flushes was recovered with low to modest losses. Solubility problems appear to be unlikely when the moles of oxalate involved are less than the total number of moles of Np due to complexation effects. The presence of significant concentrations of iron (Fe) in the solutions will further decrease the probability of Np oxalate precipitation due the formation of Fe oxalate complexes. Np oxalate solubility data in 8 M HNO{sub 3} with from one to six times as much oxalate as Np have

  13. Synthesis of labeled oxalic acid derivatives

    DOEpatents

    Martinez, Rodolfo A.; Unkefer, Clifford J.; Alvarez, Marc A.

    2004-06-22

    The present invention is directed to labeled compounds, specifically ##STR1## where each C* is selected from the group consisting of a carbon-12, i.e., .sup.12 C, or a carbon-13, i.e., .sup.13 C and at least one C* is .sup.13 C, R.sup.1 is selected from the group of C.sub.1 -C.sub.4 lower alkyl and aryl, and X is selected from the group of --NR.sup.2 R.sup.3 where R.sup.2 and R.sup.3 are each independently selected from the group of C.sub.1 -C.sub.4 lower alkyl, alkoxy and aryl, --SR.sup.4 where R.sup.4 is selected from the group of C.sub.1 -C.sub.4 lower alkyl, alkoxy and aryl, and --OR.sup.5 where R.sup.5 is selected from the group of C.sub.1 -C.sub.4 lower alkyl, alkoxy and aryl with the proviso that when R.sup.1 is methyl then R.sup.5 is other than methyl, when R.sup.1 is ethyl then R.sup.5 is other than ethyl, and when R.sup.1 is benzyl then R.sup.5 is other than benzyl.

  14. Structural variability in neptunium(V) oxalate compounds: synthesis and structural characterization of Na2NpO2(C2O4)OH.H2O.

    PubMed

    Bean, Amanda C; Garcia, Eduardo; Scott, Brian L; Runde, Wolfgang

    2004-10-01

    Reaction of a (237)Np(V) stock solution in the presence of oxalic acid, calcium chloride, and sodium hydroxide under hydrothermal conditions produces single crystals of a neptunium(V) oxalate, Na(2)NpO(2)(C(2)O(4))OH.H(2)O. The structure consists of one-dimensional chains running down the a axis and is the first example of a neptunium(V) oxalate compound containing hydroxide anions.

  15. Isoquercitrin Esters with Mono- or Dicarboxylic Acids: Enzymatic Preparation and Properties

    PubMed Central

    Vavříková, Eva; Langschwager, Fanny; Jezova-Kalachova, Lubica; Křenková, Alena; Mikulová, Barbora; Kuzma, Marek; Křen, Vladimír; Valentová, Kateřina

    2016-01-01

    A series of isoquercitrin (quercetin-3-O-β-d-glucopyranoside) esters with mono- or dicarboxylic acids was designed to modulate hydro- and lipophilicity and biological properties. Esterification of isoquercitrin was accomplished by direct chemoenzymatic reaction using Novozym 435 (lipase from Candida antarctica), which accepted C5- to C12-dicarboxylic acids; the shorter ones, such as oxalic (C2), malonic (C3), succinic (C4) and maleic (C4) acids were not substrates of the lipase. Lipophilicity of monocarboxylic acid derivatives, measured as log P, increased with the chain length. Esters with glutaric and adipic acids exhibited hydrophilicity, and the dodecanedioic acid hemiester was more lipophilic. All derivatives were less able to reduce Folin–Ciocalteau reagent (FCR) and scavenge DPPH (1,1-diphenyl-2-picrylhydrazyl) than isoquercitrin; ABTS (2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)) radical-scavenging activity was comparable. Dodecanoate and palmitate were the least active in FCR and ABTS scavenging; dodecanoate and hemiglutarate were the strongest DPPH scavengers. In contrast, most derivatives were much better inhibitors of microsomal lipoperoxidation than isoquercitrin; butyrate and hexanoate were the most efficient. Anti-lipoperoxidant activity of monocarboxylic derivatives, except acetates, decreased with increasing aliphatic chain. The opposite trend was noted for dicarboxylic acid hemiesters, isoquercitrin hemidodecanedioate being the most active. Overall, IQ butyrate, hexanoate and hemidodecanedioate are the most promising candidates for further studies. PMID:27338349

  16. Isoquercitrin Esters with Mono- or Dicarboxylic Acids: Enzymatic Preparation and Properties.

    PubMed

    Vavříková, Eva; Langschwager, Fanny; Jezova-Kalachova, Lubica; Křenková, Alena; Mikulová, Barbora; Kuzma, Marek; Křen, Vladimír; Valentová, Kateřina

    2016-01-01

    A series of isoquercitrin (quercetin-3-O-β-d-glucopyranoside) esters with mono- or dicarboxylic acids was designed to modulate hydro- and lipophilicity and biological properties. Esterification of isoquercitrin was accomplished by direct chemoenzymatic reaction using Novozym 435 (lipase from Candida antarctica), which accepted C₅- to C12-dicarboxylic acids; the shorter ones, such as oxalic (C₂), malonic (C₃), succinic (C₄) and maleic (C₄) acids were not substrates of the lipase. Lipophilicity of monocarboxylic acid derivatives, measured as log P, increased with the chain length. Esters with glutaric and adipic acids exhibited hydrophilicity, and the dodecanedioic acid hemiester was more lipophilic. All derivatives were less able to reduce Folin-Ciocalteau reagent (FCR) and scavenge DPPH (1,1-diphenyl-2-picrylhydrazyl) than isoquercitrin; ABTS (2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)) radical-scavenging activity was comparable. Dodecanoate and palmitate were the least active in FCR and ABTS scavenging; dodecanoate and hemiglutarate were the strongest DPPH scavengers. In contrast, most derivatives were much better inhibitors of microsomal lipoperoxidation than isoquercitrin; butyrate and hexanoate were the most efficient. Anti-lipoperoxidant activity of monocarboxylic derivatives, except acetates, decreased with increasing aliphatic chain. The opposite trend was noted for dicarboxylic acid hemiesters, isoquercitrin hemidodecanedioate being the most active. Overall, IQ butyrate, hexanoate and hemidodecanedioate are the most promising candidates for further studies. PMID:27338349

  17. 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.

  18. Regional differences in oxalate absorption by rat intestine: evidence for excessive absorption by the colon in steatorrhoea.

    PubMed Central

    Saunders, D R; Sillery, J; McDonald, G B

    1975-01-01

    Clinical studies suggest that steatorrhoea can be associated with excessive absorption of dietary oxalate. We examined the influence of bile salts, Ca++, and long-chain fatty acid on the absorption of oxalate and water by rat intestine in vivo. Absorption was measured under steady-state conditions during single-pass infusions. Each intestinal segment served as its own control. In jejunum, 10 mM taurocholate, the principal salt in rat bile, depressed absorption of oxalate and water. Absorption was not depressed further by Ca++ or linoleic acid. In ileum, 10 mM taurocholate did not inhibit absorption. Linoleic acid, 2 mM, depressed absorption of both oxalate and water. In colon 10 mM taurocholate decreased absorption. Net water transport was depressed further when linoleic acid was added to the infusion, but oxalate absorption was enhanced. Ca++ negated these effects of linoleic acid. It is concluded that long-chain fatty acids may enhance the absorption of oxalate from the rat colon. This observation may be relevant to understanding hyperoxaluria in patients with steatorrhoea. PMID:1158192

  19. Mechanistic characterization of a bacterial malonate semialdehyde decarboxylase: identification of a new activity on the tautomerase superfamily.

    PubMed

    Poelarends, Gerrit J; Johnson, William H; Murzin, Alexey G; Whitman, Christian P

    2003-12-01

    Malonate semialdehyde decarboxylase (MSAD) has been identified as the protein encoded by the orf130 gene from Pseudomonas pavonaceae 170 on the basis of the genomic context of the gene as well as its ability to catalyze the decarboxylation of malonate semialdehyde to generate acetaldehyde. The enzyme is found in a degradative pathway for the xenobiotic nematocide trans-1,3-dichloropropene. MSAD has no sequence homology to previously characterized decarboxylases, but the presence of a conserved motif (Pro1-(X)8 -Gly-Arg11-X-Asp-X-Gln) in its N-terminal region suggested a relationship to the tautomerase superfamily. Sequence analysis identified Pro1 and Arg75 as potential active site residues that might be involved in the MSAD activity. The results of site-directed mutagenesis experiments confirmed the importance of these residues to activity and provided further evidence to implicate MSAD as a new member of the tautomerase superfamily. MSAD is the first identified decarboxylase in the superfamily and is possibly the first characterized member of a new and distinct family within this superfamily. Malonate semialdehyde is analogous to a beta-keto acid, and enzymes that catalyze the decarboxylation of these acids generally utilize metal ion catalysis, a Schiff base intermediate, or polarization of the carbonyl group by hydrogen bonding and/or electrostatic interactions. A mechanistic analysis shows that the rate of the reaction is not affected by the presence of a metal ion or EDTA while the incubation of MSAD with the substrate in the presence of sodium cyanoborohydride results in the irreversible inactivation of the enzyme. The site of modification is Pro1. These observations are consistent with the latter two mechanisms, but do not exclude the first mechanism. Based on the sequence analysis, the outcome of the mutagenesis and mechanistic experiments, and the roles determined for Pro1 and the conserved arginine in all tautomerase superfamily members characterized

  20. Hausmannite (Mn3O4) conversion to manganite (γ-MnOOH) in dilute oxalate solution

    USGS Publications Warehouse

    Lind, Carol J.

    1988-01-01

    Oxalic acid retards the alteration of Mn3O4 to γ-MnOOH during aging at pH 7.4 ?? 0.2 in well-aerated, abiotic suspensions that contain 4.4 ?? 10-3 M total Mn. In solutions of 1.25 ?? 10-3 M oxalate and greater, about 15% of the initial Mn3O4 altered to ??-MnOOH by day 10, and in solutions of 6.7 ?? 10-4 M oxalate, about 45% altered to ??-MnOOH by day 67. Although precipitation continued through day 365, the degree of conversion remained the same as at day 10 and day 67, respectively. In oxalate-free suspensions, the conversion was about 80% complete by day 67 and 100% by day 109. Oxalate complexed most of the dissolved divalent Mn, lowered the free Mn(II) and MnSO40 concentrations, but increased the total dissolved Mn. Steric hindrance of surface reactions by a suggested manganese oxalate layer on the Mn3O4 surface may explain the blockage of the oxidation cycle.

  1. 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

  2. Effect of different cooking methods on vegetable oxalate content.

    PubMed

    Chai, Weiwen; Liebman, Michael

    2005-04-20

    Approximately 75% of all kidney stones are composed primarily of calcium oxalate, and hyperoxaluria is a primary risk factor for this disorder. Nine types of raw and cooked vegetables were analyzed for oxalate using an enzymatic method. There was a high proportion of water-soluble oxalate in most of the tested raw vegetables. Boiling markedly reduced soluble oxalate content by 30-87% and was more effective than steaming (5-53%) and baking (used only for potatoes, no oxalate loss). An assessment of the oxalate content of cooking water used for boiling and steaming revealed an approximately 100% recovery of oxalate losses. The losses of insoluble oxalate during cooking varied greatly, ranging from 0 to 74%. Because soluble sources of oxalate appear to be better absorbed than insoluble sources, employing cooking methods that significantly reduce soluble oxalate may be an effective strategy for decreasing oxaluria in individuals predisposed to the development of kidney stones.

  3. Synthesis and evaluation of malonate-based inhibitors of phosphosugar-metabolizing enzymes: class II fructose-1,6-bis-phosphate aldolases, type I phosphomannose isomerase, and phosphoglucose isomerase.

    PubMed

    Desvergnes, Stéphanie; Courtiol-Legourd, Stéphanie; Daher, Racha; Dabrowski, Maciej; Salmon, Laurent; Therisod, Michel

    2012-02-15

    In the design of inhibitors of phosphosugar metabolizing enzymes and receptors with therapeutic interest, malonate has been reported in a number of cases as a good and hydrolytically-stable surrogate of the phosphate group, since both functions are dianionic at physiological pH and of comparable size. We have investigated a series of malonate-based mimics of the best known phosphate inhibitors of class II (zinc) fructose-1,6-bis-phosphate aldolases (FBAs) (e.g., from Mycobacterium tuberculosis), type I (zinc) phosphomannose isomerase (PMI) from Escherichia coli, and phosphoglucose isomerase (PGI) from yeast. In the case of FBAs, replacement of one phosphate by one malonate on a bis-phosphorylated inhibitor (1) led to a new compound (4) still showing a strong inhibition (K(i) in the nM range) and class II versus class I selectivity (up to 8×10(4)). Replacement of the other phosphate however strongly affected binding efficiency and selectivity. In the case of PGI and PMI, 5-deoxy-5-malonate-D-arabinonohydroxamic acid (8) yielded a strong decrease in binding affinities when compared to its phosphorylated parent compound 5-phospho-D-arabinonohydroxamic acid (2). Analysis of the deposited 3D structures of the kinetically evaluated enzymes complexed to the phosphate-based inhibitors indicate that malonate could be a good phosphate surrogate only if phosphate is not tightly bound at the enzyme active site, such as in position 7 of compound 1 for FBAs. These observations are of importance for further design of inhibitors of phosphorylated-compounds metabolizing enzymes with therapeutic interest.

  4. Magnetic Compensation in the Bimetallic Oxalates

    SciTech Connect

    Reis, Peter L; Fishman, Randy Scott; Reboredo, Fernando A; Moreno, Juana

    2008-01-01

    Bimetallic oxalates are layered molecule-based magnets with either ferromagnetic or antiferromagnetic interactions between transition metals M(II) and M'(III) on an open honeycomb lattice. Some Fe(II)Fe(III) bimetallic oxalates exhibit magnetic compensation (MC) at a compensation temperature Tcomp ≈ 30 K below the ferrimagnetic transition temperature Tc ≈ 45 K. To see if MC is possible in other bimetallic oxalates, we construct a theoretical model for bimetallic oxalates that exhibit antiferromagnetic interactions. By varying the M(II) and M'(III) average orbital angular momentum, which can be controlled by the choice of interlayer cations, we have found regions of MC in the families M(II)Mn(III) with M = Fe, Co, or Ni and V(II)M'(III) with M' = Cr or V but not in the family M(II)Ru(III) with M = Fe or Cu.

  5. Chaga mushroom-induced oxalate nephropathy.

    PubMed

    Kikuchi, Yuko; Seta, Koichi; Ogawa, Yayoi; Takayama, Tatsuya; Nagata, Masao; Taguchi, Takashi; Yahata, Kensei

    2014-06-01

    Chaga mushrooms have been used in folk and botanical medicine as a remedy for cancer, gastritis, ulcers, and tuberculosis of the bones. A 72-year-old Japanese female had been diagnosed with liver cancer 1 year prior to presenting at our department. She underwent hepatectomy of the left lobe 3 months later. Chaga mushroom powder (4 - 5 teaspoons per day) had been ingested for the past 6 months for liver cancer. Renal function decreased and hemodialysis was initiated. Renal biopsy specimens showed diffuse tubular atrophy and interstitial fibrosis. Oxalate crystals were detected in the tubular lumina and urinary sediment and oxalate nephropathy was diagnosed. Chaga mushrooms contain extremely high oxalate concentrations. This is the first report of a case of oxalate nephropathy associated with ingestion of Chaga mushrooms.

  6. Defluoridation of water using dicarboxylic acids mediated chitosan-polyaniline/zirconium biopolymeric complex.

    PubMed

    Muthu Prabhu, Subbaiah; Meenakshi, Sankaran

    2016-04-01

    The present investigation describes the preparation of hydrogen bonded chitosan-polyaniline/zirconium biopolymeric matrix by grafting method under dicarboxylic acid medium for the removal of fluoride, first time. Herein, the dicarboxylic acids, oxalic acid, malonic acid, succinic acid were used as medium. The synthesized complex was characterized by usual analytical techniques like FTIR, XRD, SEM and EDAX analysis. From the batch equilibrium experiments, the maximum defluoridation capacity (DC) was found to be 8.713 mg/g at room temperature with the minimum contact time of 24 min at 100mg of the sorbent dosage. The temperature study results of adsorption kinetics showed the adsorption behavior could be better described by the pseudo-second-order equation than pseudo-first-order kinetic model. The adsorption isotherm was well fitted by the Freundlich equation rather than Langmuir and D-R isotherms. The mechanism of fluoride removal was ligand exchange at neutral pH and electrostatic attraction at acidic pH of the medium. Regeneration studies were carried out to identify the best regenerant which makes the process cost-effective. Conclusions of this work demonstrate the potential applicability of the dicarboxylic acid mediated chitosan-polyaniline/zirconium complex as an effective adsorbent for fluoride removal from water. PMID:26706844

  7. Defluoridation of water using dicarboxylic acids mediated chitosan-polyaniline/zirconium biopolymeric complex.

    PubMed

    Muthu Prabhu, Subbaiah; Meenakshi, Sankaran

    2016-04-01

    The present investigation describes the preparation of hydrogen bonded chitosan-polyaniline/zirconium biopolymeric matrix by grafting method under dicarboxylic acid medium for the removal of fluoride, first time. Herein, the dicarboxylic acids, oxalic acid, malonic acid, succinic acid were used as medium. The synthesized complex was characterized by usual analytical techniques like FTIR, XRD, SEM and EDAX analysis. From the batch equilibrium experiments, the maximum defluoridation capacity (DC) was found to be 8.713 mg/g at room temperature with the minimum contact time of 24 min at 100mg of the sorbent dosage. The temperature study results of adsorption kinetics showed the adsorption behavior could be better described by the pseudo-second-order equation than pseudo-first-order kinetic model. The adsorption isotherm was well fitted by the Freundlich equation rather than Langmuir and D-R isotherms. The mechanism of fluoride removal was ligand exchange at neutral pH and electrostatic attraction at acidic pH of the medium. Regeneration studies were carried out to identify the best regenerant which makes the process cost-effective. Conclusions of this work demonstrate the potential applicability of the dicarboxylic acid mediated chitosan-polyaniline/zirconium complex as an effective adsorbent for fluoride removal from water.

  8. Characterization of calcium oxalate biominerals in some (non-Cactaceae) succulent plant species.

    PubMed

    Monje, Paula V; Baran, Enrique J

    2010-01-01

    The water-accumulating leaves of crassulacean acid metabolism plants belonging to five different families were investigated for the presence of biominerals by infrared spectroscopic and microscopic analyses. Spectroscopic results revealed that the mineral present in succulent species of Agavaceae, Aizoaceae, and Asphodelaceae was calcium oxalate monohydrate (whewellite, CaC2O4 x H2O). Crystals were predominantly found as raphides or solitary crystals of various morphologies. However, representative Crassulaceae members and a succulent species of Asteraceae did not show the presence of biominerals. Overall, these results suggest no correlation between calcium oxalate generation and crassulacean acid metabolism in succulent plants.

  9. Modeling the Adsorption of Oxalate onto Montmorillonite.

    PubMed

    Ramos, M Elena; Emiroglu, Caglayan; García, David; Sainz-Díaz, C Ignacio; Huertas, F Javier

    2015-11-01

    In this work, a multiscale modeling of the interaction of oxalate with clay mineral surfaces from macroscale thermodynamic equilibria simulations to atomistic calculations is presented. Previous results from macroscopic adsorption data of oxalate on montmorillonite in 0.01 M KNO3 media at 25 °C within the pH range from 2.5 to 9 have been used to develop a surface complexation model. The experimental adsorption edge data were fitted using the triple-layer model (TLM) with the aid of the FITEQL 4.0 computer program. Surface complexation of oxalate is described by two reactions: >AlOH + Ox(2-) + 2H(+) = >AlOxH + H2O (log K = 14.39) and >AlOH + Ox(2-) + H(+) = >AlOx(-) + H2O (log K = 10.39). The monodentate complex >AlOxH dominated adsorption below pH 4, and the bidentate complex >AlOx(-) was predominant at higher pH values. Both of the proposed inner-sphere oxalate species are qualitatively consistent with previously published diffuse reflectance FTIR spectroscopic results for oxalate on montmorillonite edge surface (Chem. Geol. 2014, 363, 283-292). Atomistic computational studies have been performed to understand the interactions at the molecular level between adsorbates and mineral surface, showing the atomic structures and IR frequency shifts of the adsorption complexes of oxalate with the edge surface of a periodic montmorillonite model. PMID:26444928

  10. Genetics Home Reference: combined malonic and methylmalonic aciduria

    MedlinePlus

    ... plays a role in the formation (synthesis) of fatty acids. Fatty acids are building blocks used to make fats (lipids). ... malonyl-CoA, which is the first step of fatty acid synthesis in cellular structures called mitochondria . Based on ...

  11. Interconversion of biologically important carboxylic acids by radiation

    NASA Technical Reports Server (NTRS)

    Negron-Mendoza, A.; Ponnamperuma, C.

    1978-01-01

    The interconversion of a group of biologically important polycarboxylic acids (acetic, fumaric, malic, malonic, succinic, citric, isocitric, tricarballylic) under gamma-ray or ultraviolet radiation was investigated. The formation of high molecular weight compounds was observed in all cases. Succinic acid was formed in almost all radiolysis experiments. Citric, malonic, and succinic acids appeared to be relatively insensitive to radiation. Interconversion of the polycarboxylic acids studied may have occurred under the effect of radiation in the prebiotic earth.

  12. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-07-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  13. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-01-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic aerosols (BA), for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2) and malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment, except for ω-oxooctanoic acid (ωC8) that showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids dominates their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  14. Ionothermal synthesis of two oxalate-bridged lanthanide(III) chains with slow magnetization relaxation by using a deep eutectic solvent.

    PubMed

    Meng, Yan; Liu, Jun-Liang; Zhang, Ze-Min; Lin, Wei-Quan; Lin, Zhuo-Jia; Tong, Ming-Liang

    2013-09-28

    Two novel isostructural oxalate-bridged lanthanide(III) chains, (choline)[Ln(ox)(H2O)3Cl]Cl·H2O (Ln = Dy/Er), were first obtained ionothermally by using a choline chloride-oxalic acid eutectic mixture as both solvent and structure-directing agent, both of which show field-induced slow relaxation of magnetization.

  15. Ionothermal synthesis of two oxalate-bridged lanthanide(III) chains with slow magnetization relaxation by using a deep eutectic solvent.

    PubMed

    Meng, Yan; Liu, Jun-Liang; Zhang, Ze-Min; Lin, Wei-Quan; Lin, Zhuo-Jia; Tong, Ming-Liang

    2013-09-28

    Two novel isostructural oxalate-bridged lanthanide(III) chains, (choline)[Ln(ox)(H2O)3Cl]Cl·H2O (Ln = Dy/Er), were first obtained ionothermally by using a choline chloride-oxalic acid eutectic mixture as both solvent and structure-directing agent, both of which show field-induced slow relaxation of magnetization. PMID:23903323

  16. Effects of surface coordination on the temperature-programmed desorption of oxalate from goethite

    SciTech Connect

    Boily, Jean F.; Szanyi, Janos; Felmy, Andrew R.

    2007-11-15

    The temperature-programmed desorption (TPD) of weakly-bound, hydrogen-bonded and metal-bonded oxalate complexes at the goethite surface was investigated in the 300-900 K range with concerted Fourier Transform Infrared (FTIR) measurements (TPD-FTIR). These reactions took place with the concomitant dehydroxylation reaction of goethite to hematite and decarbonation of bulk-occluded carbonate. The measurements revealed three important stages of desorption. Stage I (300-440 K) corresponds to the desorption of weakly-and/or un-bound oxalate molecules in the goethite powder with a thermal decomposition reaction pathway characteristic of oxalic acid. Stage II (440-520 K) corresponds to a thermally-driven dehydration of hydrogen-bonded surface complexes, leading to a partial desorption via oxalic acid thermal decomposition pathways and to a partial conversion to metal-bonded surface complexes. This latter mechanism led to the increase in FTIR bands characteristic of these complexes. Finally, Stage III (520-660 K) corresponds to the thermal decomposition of the metal-bonded oxalate complex, proceeding through a 2 electron reduction pathway.

  17. Therapeutic effect of Xue Niao An on glyoxylate-induced calcium oxalate crystal deposition based on urinary metabonomics approach

    PubMed Central

    Peng, Zhongjiang; Chen, Wei; Gao, Songyan; Su, Li; Li, Na; Wang, Li; Lou, Ziyang; Dong, Xin; Guo, Zhiyong

    2014-01-01

    The anti-nephrolithiasis effect of Xue Niao An (XNA) capsules is explored by analyzing urine metabolic profiles in mouse models, with ultra-high performance liquid chromatography quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS). An animal model of calcium oxalate crystal renal deposition was established in mice by intra-abdominal injection of glyoxylate. Then, treatment with XNA by intra-gastric administration was performed. At the end of the study, calcium deposition in kidney was measured by Von Kossa staining under light microscopy, and the Von Kossa staining changes showed that XNA significantly alleviated the calcium oxalate crystal deposition. Meanwhile, urine samples for fifteen metabolites, including amino acids and fatty acids, with significant differences were detected in the calcium oxalate group, while XNA treatment attenuated metabolic imbalances. Our study indicated that the metabonomic strategy provided comprehensive insight on the metabolic response to XNA treatment of rodent renal calcium oxalate deposition. PMID:25411524

  18. Adsorption of Small Weak Organic Acids on Goethite: Modeling of Mechanisms

    PubMed

    Filius; Hiemstra; Van Riemsdijk WH

    1997-11-15

    The adsorption of lactate, oxalate, malonate, phthalate, and citrate has been determined experimentally as a function of concentration, pH, and ionic strength. The data have been described with the CD-MUSIC model of Hiemstra and Van Riemsdijk [J. Colloid Interface Sci. 179, 488-508 (1996)] which allows a distribution of charge of the organic molecule over the surface and the Stern layer. Simultaneously, the concentration, pH, and salt dependency as well as the basic charging behavior of goethite could be described well. On the basis of model calculations, a distinction is made between inner and outer sphere complexation of weak organic acids by goethite. The results indicate that the affinity of the organic acids is dominated by the electrostatic attraction. The intrinsic affinity constants for the exchange reaction of surface water groups and organic acids, expressed per bond, increases with increasing number of reactive groups on the organic molecule. Ion pair formation between noncoordinated carboxylic groups of adsorbed organic acids and cations of the background electrolyte proved to be important for the salt dependency. The knowledge obtained may contribute to the interpretation of the binding of larger organic acids like fulvic and humic acids. Copyright 1997 Academic Press. Copyright 1997Academic Press PMID:9441638

  19. Adsorption of small weak organic acids on goethite: Modeling of mechanisms

    SciTech Connect

    Filius, J.D.; Hiemstra, T.; Riemsdijk, W.H. Van

    1997-11-15

    The adsorption of lactate, oxalate, malonate, phthalate, and citrate has been determined experimentally as a function of concentration, pH, and ionic strength. The data have been described with the CD-MUSIC model of Hiemstra and Van Riemsdijk which allows a distribution of charge of the organic molecule over the surface and the Stern layer. Simultaneously, the concentration, pH, and salt dependency as well as the basic charging behavior of goethite could be described well. On the basis of model calculations, a distinction is made between inner and outer sphere complexation of weak organic acids by goethite. The results indicate that the affinity of the organic acids is dominated by the electrostatic attraction. The intrinsic affinity constants for the exchange reaction of surface water groups and organic acids, expressed per bond, increases with increasing number of reactive groups on the organic molecule. Ion pair formation between noncoordinated carboxylic groups of adsorbed organic acids and cations of the background electrolyte proved to be important for the salt dependency. The knowledge obtained may contribute to the interpretation of the binding of larger organic acids like fulvic and humic acids.

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

    SciTech Connect

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

    2015-07-15

    Two 2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonato and oxalic acid bridged coordination polymers (H{sub 2}en)[Co{sub 3}(H{sub 2}zdn){sub 2}(ox)(H{sub 2}O){sub 2}] (1) and Cd{sub 2}(H{sub 2}zdn)(ox){sub 0.5}(H{sub 2}O) (2) (2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonic acid=H{sub 5}zdn; oxalic acid=H{sub 2}ox) 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 H{sub 5}zdn 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. - Graphical abstract: Linked by oxalate, two zoledronate-based metal–organic frameworks are synthesized, which exhibits the different frameworks. Magnetism and luminescent properties have been studied. The weak antiferromagnetic coupling is conducted in 1. - Highlights: • Compound 1 and 2 are first linked by oxalate anion based on zoledronic acid. • Compound 1 generates a classic “dia Diamond” (6{sup 6}) topology. • Compound 2 exhibits a (4{sup 4}·6{sup 2})(4{sup 4}·6{sup 6}) topology. • Magnetism and luminescent properties of 1 and 2 have been studied, respectively.

  1. Seasonal variations and source identification of selected organic acids associated with PM10 in the coastal area of Southeastern China

    NASA Astrophysics Data System (ADS)

    Wu, Shui-Ping; Schwab, James; Liu, Bi-Lian; Li, Tsung-Chang; Yuan, Chung-Shin

    2015-03-01

    PM10 aerosols from the coastal area of Southeastern China were collected from April 2010 to March 2011 and were measured for C2-C10 dicarboxylic acids, phthalic acids (Ph) and five fatty acids (palmitic, stearic, oleic, linoleic and elaidic acids). For all sites and seasons, molecular distributions of diacids were always characterized by a predominance of oxalic acid (C2), with a relative abundance of 68-87%, followed by malonic acid (C3) and by either succinic acid (C4) or phthalic acid (Ph). This observed molecular composition was different from that in Chinese megacities where Ph was significantly higher than C3 and C4 diacids, which was likely due to the less intensive traffic emissions in the coastal area. Seasonal means of total diacids ranged between 394 and 547 ng m- 3 at the coastal urban sites and between 163 and 245 ng m- 3 at off-island sites. These levels were much lower than those reported in Chinese megacities (668-1568 ng m- 3) and slightly lower than those in Jeju Island, Korea (464-744 ng m- 3) but higher than those in marine and continental background locations. In all seasons, saturated fatty acids were significantly higher than unsaturated fatty acids due to their greater photochemical stabilities in the atmosphere. Most organic acids showed higher levels in spring and winter and lower levels in summer and fall, which was likely due to the influence of transport and meteorology. The diagnostic ratios of malonic acid to succinic acid (C3/C4), adipic acid to azelaic acid (C6/C9) and phthalic acid to azelaic acid (Ph/C9) were significantly higher in summer than in winter. These diagnostic ratios in the sampled ambient aerosols were completely different from those in primary emissions, suggesting the importance of photochemical production - especially in summer. The diurnal variations of diacids and fatty acid as well as the diagnostic ratios are associated with higher solar radiation and anthropogenic activities during the daytime. Principal

  2. 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

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

    SciTech Connect

    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 precipitation 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 beta dec

  4. Alkylidene malonates and α,β-unsaturated α'-hydroxyketones as practical substrates for vinylogous Friedel-Crafts alkylations in water catalysed by scandium(III) triflate/SDS.

    PubMed

    Oelerich, Jens; Roelfes, Gerard

    2015-03-01

    Alkylidene malonates and α,β-unsaturated α'-hydroxyketones are demonstrated to be efficient classes of electrophiles for the scandium(III) triflate/sodium dodecyl sulphate (SDS) catalysed vinylogous Friedel-Crafts alkylation of indoles and pyrroles in water. These substrates contain an easily removable auxiliary group that increases affinity for the catalytic metal ion in such a way that they can compete with water for binding to the catalytic metal ion. Thus, alkylidene malonates and α,β-unsaturated α'-hydroxyketones are attractive substitutes for, e.g., α,β-unsaturated carboxylic acids and -esters, which in aqueous media are not reactive enough in these reactions. The combination of Lewis acid and SDS in catalysis results in considerable acceleration of the reaction in water compared to organic solvents. The method presented is attractive because the reactions are fast, experimentally straightforward and give rise to high yields of products.

  5. Alkylidene malonates and α,β-unsaturated α'-hydroxyketones as practical substrates for vinylogous Friedel-Crafts alkylations in water catalysed by scandium(III) triflate/SDS.

    PubMed

    Oelerich, Jens; Roelfes, Gerard

    2015-03-01

    Alkylidene malonates and α,β-unsaturated α'-hydroxyketones are demonstrated to be efficient classes of electrophiles for the scandium(III) triflate/sodium dodecyl sulphate (SDS) catalysed vinylogous Friedel-Crafts alkylation of indoles and pyrroles in water. These substrates contain an easily removable auxiliary group that increases affinity for the catalytic metal ion in such a way that they can compete with water for binding to the catalytic metal ion. Thus, alkylidene malonates and α,β-unsaturated α'-hydroxyketones are attractive substitutes for, e.g., α,β-unsaturated carboxylic acids and -esters, which in aqueous media are not reactive enough in these reactions. The combination of Lewis acid and SDS in catalysis results in considerable acceleration of the reaction in water compared to organic solvents. The method presented is attractive because the reactions are fast, experimentally straightforward and give rise to high yields of products. PMID:25604240

  6. Hyperoxaluria leads to dysbiosis and drives selective enrichment of oxalate metabolizing bacterial species in recurrent kidney stone endures

    PubMed Central

    Suryavanshi, Mangesh V.; Bhute, Shrikant S.; Jadhav, Swapnil D.; Bhatia, Manish S.; Gune, Rahul P.; Shouche, Yogesh S.

    2016-01-01

    Hyperoxaluria due to endogenously synthesized and exogenously ingested oxalates is a leading cause of recurrent oxalate stone formations. Even though, humans largely rely on gut microbiota for oxalate homeostasis, hyperoxaluria associated gut microbiota features remain largely unknown. Based on 16S rRNA gene amplicons, targeted metagenomic sequencing of formyl-CoA transferase (frc) gene and qPCR assay, we demonstrate a selective enrichment of Oxalate Metabolizing Bacterial Species (OMBS) in hyperoxaluria condition. Interestingly, higher than usual concentration of oxalate was found inhibitory to many gut microbes, including Oxalobacter formigenes, a well-characterized OMBS. In addition a concomitant enrichment of acid tolerant pathobionts in recurrent stone sufferers is observed. Further, specific enzymes participating in oxalate metabolism are found augmented in stone endures. Additionally, hyperoxaluria driven dysbiosis was found to be associated with oxalate content, stone episodes and colonization pattern of Oxalobacter formigenes. Thus, we rationalize the first in-depth surveillance of OMBS in the human gut and their association with hyperoxaluria. Our findings can be utilized in the treatment of hyperoxaluria associated recurrent stone episodes. PMID:27708409

  7. An Assessment of Engineered Calcium Oxalate Crystal Formation on Plant Growth and Development as a Step toward Evaluating Its Use to Enhance Plant Defense

    PubMed Central

    Nakata, Paul A.

    2015-01-01

    The establishment of new approaches to control chewing insects has been sought not only for direct use in reducing crop loss but also in managing resistance to the pesticides already in use. Engineered formation of calcium oxalate crystals is a potential strategy that could be developed to fulfill both these needs. As a step toward this development, this study investigates the effects of transforming a non-calcium oxalate crystal accumulating plant, Arabidopsis thaliana, into a crystal accumulating plant. Calcium oxalate crystal accumulating A. thaliana lines were generated by ectopic expression of a single bacterial gene encoding an oxalic acid biosynthetic enzyme. Biochemical and cellular studies suggested that the engineered A. thaliana lines formed crystals of calcium oxalate in a manner similar to naturally occurring crystal accumulating plants. The amount of calcium oxalate accumulated in leaves also reached levels similar to those measured in the leaves of Medicago truncatula in which the crystals are known to play a defensive role. Visual inspection of the different engineered lines, however, suggested a phenotypic consequence on plant growth and development with higher calcium oxalate concentrations. The restoration of a near wild-type plant phenotype through an enzymatic reduction of tissue oxalate supported this observation. Overall, this study is a first to provide initial insight into the potential consequences of engineering calcium oxalate crystal formation in non-crystal accumulating plants. PMID:26517544

  8. An Assessment of Engineered Calcium Oxalate Crystal Formation on Plant Growth and Development as a Step toward Evaluating Its Use to Enhance Plant Defense.

    PubMed

    Nakata, Paul A

    2015-01-01

    The establishment of new approaches to control chewing insects has been sought not only for direct use in reducing crop loss but also in managing resistance to the pesticides already in use. Engineered formation of calcium oxalate crystals is a potential strategy that could be developed to fulfill both these needs. As a step toward this development, this study investigates the effects of transforming a non-calcium oxalate crystal accumulating plant, Arabidopsis thaliana, into a crystal accumulating plant. Calcium oxalate crystal accumulating A. thaliana lines were generated by ectopic expression of a single bacterial gene encoding an oxalic acid biosynthetic enzyme. Biochemical and cellular studies suggested that the engineered A. thaliana lines formed crystals of calcium oxalate in a manner similar to naturally occurring crystal accumulating plants. The amount of calcium oxalate accumulated in leaves also reached levels similar to those measured in the leaves of Medicago truncatula in which the crystals are known to play a defensive role. Visual inspection of the different engineered lines, however, suggested a phenotypic consequence on plant growth and development with higher calcium oxalate concentrations. The restoration of a near wild-type plant phenotype through an enzymatic reduction of tissue oxalate supported this observation. Overall, this study is a first to provide initial insight into the potential consequences of engineering calcium oxalate crystal formation in non-crystal accumulating plants.

  9. LMWOA (low molecular weight organic acid) exudation by salt marsh plants: Natural variation and response to Cu contamination

    NASA Astrophysics Data System (ADS)

    Mucha, Ana P.; Almeida, C. Marisa R.; Bordalo, Adriano A.; Vasconcelos, M. Teresa S. D.

    2010-06-01

    This work aimed to evaluate, in vitro, the capability of roots of two salt marsh plants to release low molecular weight organic acids (LMWOAs) and to ascertain whether Cu contamination would stimulate or not organic acids exudation. The sea rush Juncus maritimus and the sea-club rush Scirpus maritimus, both from the lower Douro river estuary (NW Portugal), were used. Plants were collected seasonally, four times a year in 2004, during low tide. After sampling, plant roots were washed for removal of adherent particles and immersed for 2 h in a solution that matched salinity (3) and pH (7.5) of the pore water from the same location to obtain plant exudates. In one of the seasons, similar experiments were carried out but spiking the solution with different amounts of Cu in order to embrace the range between 0 and 1600 nM. In the final solutions as well as in sediment pore water LMWOAs were determined by high performance liquid chromatography. Plants were able to release, in a short period of time, relatively high amounts of LMWOAs (oxalate, citrate, malate, malonate, and succinate). In the sediment pore water oxalate, succinate and acetate were also detected. Therefore, plant roots probably contributed to the presence of some of these organic compounds in pore water. Exudation differed between the plant species and also showed some seasonally variation, particularly for S. maritimus. The release of oxalate by J. maritimus increased with Cu increase in the media. However, exudation of the other LMWOAs did not seem to be stimulated by Cu contamination in the media. This fact is compatible with the existence of alternative internal mechanisms for Cu detoxification, as denoted by the fact that in media contaminated with Cu both plant species accumulated relatively high amounts (29-83%) of the initially dissolved Cu. This study expands our knowledge on the contribution of globally dominant salt marsh plants to the release of LMWOAs into the environment.

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

    SciTech Connect

    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 ozone 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 decreased

  11. SmI(2)-mediated carbon-carbon bond fragmentation in alpha-aminomethyl malonates.

    PubMed

    Xu, Qiongfeng; Cheng, Bin; Ye, Xinshan; Zhai, Hongbin

    2009-09-17

    A new and efficient samarium diiodide-promoted carbon-carbon bond fragmentation reaction of alpha-aminomethyl malonates, taking place normally at room temperature and generating the corresponding deaminomethylation products in 74-94% yields, is reported. The presence of the amino group is necessary for the success of the current transformation.

  12. Statistical Thermodynamic Model for Surface Tension of Aqueous Organic Acids with Consideration of Partial Dissociation.

    PubMed

    Boyer, Hallie C; Dutcher, Cari S

    2016-06-30

    With statistical mechanics, an isotherm-based surface tension model for single solute aqueous solutions was derived previously (Wexler et al. J. Phys. Chem. Lett. 2013) for the entire concentration range, from infinite dilution to pure liquid solute, as a function of solute activity. In recent work (Boyer et al. J. Phys. Chem. Lett. 2015), empirical model parameters were reduced through physicochemical interpretations of both electrolyte and organic solutes, enabling surface tension predictions for systems where there is little or no data. The prior binary model is extended in the current work for the first time to treat multicomponent systems to predict surface tensions of partially dissociating organic acids (acetic, butyric, citric, formic, glutaric, maleic, malic, malonic, oxalic, propionic, and succinic acids). These organic acids are especially applicable to the study of atmospheric aqueous aerosols, due to their abundance in the atmosphere. In the model developed here, surface tension depends explicitly on activities of both the neutral organic and deprotonated components of the acid. The relative concentrations of the nondissociated and dissociated mole fractions are found using known dissociation constants. Model parameters strongly depend on molecular size, number of functional groups, O:C ratio, and number of carbons. For all organic acids in this study, fully predictive modeling of surface tensions is demonstrated.

  13. Statistical Thermodynamic Model for Surface Tension of Aqueous Organic Acids with Consideration of Partial Dissociation.

    PubMed

    Boyer, Hallie C; Dutcher, Cari S

    2016-06-30

    With statistical mechanics, an isotherm-based surface tension model for single solute aqueous solutions was derived previously (Wexler et al. J. Phys. Chem. Lett. 2013) for the entire concentration range, from infinite dilution to pure liquid solute, as a function of solute activity. In recent work (Boyer et al. J. Phys. Chem. Lett. 2015), empirical model parameters were reduced through physicochemical interpretations of both electrolyte and organic solutes, enabling surface tension predictions for systems where there is little or no data. The prior binary model is extended in the current work for the first time to treat multicomponent systems to predict surface tensions of partially dissociating organic acids (acetic, butyric, citric, formic, glutaric, maleic, malic, malonic, oxalic, propionic, and succinic acids). These organic acids are especially applicable to the study of atmospheric aqueous aerosols, due to their abundance in the atmosphere. In the model developed here, surface tension depends explicitly on activities of both the neutral organic and deprotonated components of the acid. The relative concentrations of the nondissociated and dissociated mole fractions are found using known dissociation constants. Model parameters strongly depend on molecular size, number of functional groups, O:C ratio, and number of carbons. For all organic acids in this study, fully predictive modeling of surface tensions is demonstrated. PMID:27219322

  14. A Novel Methodology for Processing of Plutonium-Bearing Waste as Ammonium Plutonium(III)-Oxalate

    SciTech Connect

    Sali, Sanjay Krishnarao; Noronha, Donal Marshal; Mhatre, Hemakant Ramkrishna; Mahajan, Murlidhar Anna; Chander, Keshav; Aggarwal, Suresh Kumar; Venugopal, Venkatarama

    2005-09-15

    A novel methodology has been developed for the recovery of Pu from different types of waste solutions generated during various operations involved in the chemical quality control/assurance of nuclear fuels. The method is based on the precipitation of Pu as ammonium plutonium(III)-oxalate and involves the adjustment of acidity of the Pu solution to 1 N, the addition of ascorbic acid (0.05 M) to reduce Pu to Pu(III), followed by the addition of (NH{sub 4}){sub 2}SO{sub 4} (0.5 M) and a stoichiometric amount of saturated oxalic acid maintaining a 0.2 M excess of oxalic acid concentration in the supernatant. The precipitate was characterized by X-ray powder diffraction and thermal and chemical analysis and was found to have the composition NH{sub 4}Pu(C{sub 2}O{sub 4}){sub 2}.3H{sub 2}O. This compound can be easily decomposed to PuO{sub 2} on heating in air at 823 K. Decontamination factors of U, Fe, and Cr determined showed quantitative removal of these ions during the precipitation of Pu as ammonium plutonium(III)-oxalate.A semiautomatic assembly based on the transfer of solutions by suction arrangement was designed and fabricated for processing large volumes of Pu solution. This assembly reduced the corrosion of the glove-box material and offered the advantage of lower radiation exposure to the working personnel.

  15. Urine glycoprotein crystal growth inhibitors. Evidence for a molecular abnormality in calcium oxalate nephrolithiasis.

    PubMed Central

    Nakagawa, Y; Abram, V; Parks, J H; Lau, H S; Kawooya, J K; Coe, F L

    1985-01-01

    One reason that some people are prone to calcium oxalate nephrolithiasis is that they produce urine that is subnormal in its ability to inhibit the growth of calcium oxalate crystals. We have identified in human urine a glycoprotein (GCI) that inhibits calcium oxalate crystal growth strongly, and at low concentrations (10(-7) M); in this study, we have isolated GCI molecules from the urine of normal people and patients with calcium oxalate stones. GCI from stone formers is abnormal in three ways: it contains no detectable gamma-carboxyglutamic acid (Gla), whereas normal GCI contains 2-3 residues of Gla per mole; about half of the GCI in urine of patients inhibits crystal growth 4-20 times less than normal GCI as judged by its performance in a kinetic growth assay, in vitro; at the air-water interface, patient GCI has a film collapse pressure approximately half of normal. GCI molecules from the urine of patients with calcium oxalate nephrolithiasis are intrinsically abnormal, and these abnormalities could play a role in the genesis of stones. PMID:4056037

  16. Complexation of Am(III) by oxalate in NaClO{sub 4} media

    SciTech Connect

    Choppin, G.R.; Chen, J.F.

    1995-09-01

    The complexation of Am(III) by oxalate has been investigated in solutions of NaClO{sub 4} up to 9.0 M ionic strength at 25{degrees}C. The dissociation constants of oxalic acid were determined by potentiometric titration, while the stability constants of the Am(III)-oxalate complexation were measured by the solvent extraction technique. A thermodynamic model was constructed to predict the apparent equilibrium constants at different ionic strengths by applying the Pitzer equation using parameters for the Na{sup +}-HOx{sup -}, Na{sup +}-Ox{sup -}, AmOx{sup +}-ClO{sub 4}{sup -}, and Na{sup +}-Am(Ox){sub 2}{sup -} interactions obtained by fitting the data.

  17. Observation of superoxide production during catalysis of Bacillus subtilis oxalate decarboxylase at pH 4.

    PubMed

    Twahir, Umar T; Stedwell, Corey N; Lee, Cory T; Richards, Nigel G J; Polfer, Nicolas C; Angerhofer, Alexander

    2015-03-01

    This contribution describes the trapping of the hydroperoxyl radical at a pH of 4 during turnover of wild-type oxalate decarboxylase and its T165V mutant using the spin-trap BMPO. Radicals were detected and identified by a combination of EPR and mass spectrometry. Superoxide, or its conjugate acid, the hydroperoxyl radical, is expected as an intermediate in the decarboxylation and oxidation reactions of the oxalate monoanion, both of which are promoted by oxalate decarboxylase. Another intermediate, the carbon dioxide radical anion was also observed. The quantitative yields of superoxide trapping are similar in the wild type and the mutant while it is significantly different for the trapping of the carbon dioxide radical anion. This suggests that the two radicals are released from different sites of the protein. PMID:25526893

  18. [Effect of lectins from Azospirillum brasilense to peroxidase and oxalate oxidase activity regulation in wheat roots].

    PubMed

    Alen'kina, S A; Nikitina, V E

    2010-01-01

    Lectins were extracted from the surface of nitrogen-fixing soil bacteria Azospirillum brasilense Sp7 and from its mutant A. brasilense Sp7.2.3 defective in lectin activity. The ability oflectins to stimulate the rapid formation of hydrogen peroxide related to increase of oxalate oxidase and peroxidase activity in the roots of wheat seedlings has been demonstrated. The most rapid induced pathway of hydrogen peroxide formation in the roots of wheat seedlings was the oxalic acid oxidation by oxalate oxidase which is the effect oflectin in under 10 min in a concentration of 10 microg/ml. The obtained results show that lectins from Azospirillum are capable of inducing the adaptation processes in the roots of wheat seedlings.

  19. Observation of Superoxide Production During Catalysis of Bacillus subtilis Oxalate Decarboxylase at pH4

    PubMed Central

    Twahir, Umar T.; Stedwell, Corey N.; Lee, Cory T.; Richards, Nigel G. J.; Polfer, Nicolas C.; Angerhofer, Alexander

    2015-01-01

    This contribution describes the trapping of the hydroperoxyl radical at a pH of 4 during turnover of wild-type oxalate decarboxylase and its T165V mutant using the spin trap BMPO. Radicals were detected and identified by a combination of EPR and mass spectrometry. Superoxide, or its conjugate acid, the hydroperoxyl radical, is expected as an intermediate in the decarboxylation and oxidation reactions of the oxalate monoanion both of which are promoted by oxalate decarboxylase. Another intermediate, the carbon dioxide radical anion was also observed. The quantitative yields of superoxide trapping is similar in the wild type and the mutant while it is significantly different for the trapping of the carbon dioxide radical anion. This suggests that the two radicals are released from different sites of the protein. PMID:25526893

  20. An isotopic study of oxalate excretion in sheep.

    PubMed

    McIntosh, G H; Belling, G B

    1975-12-01

    Intravenously injected 14C labelled oxalate was rapidly removed from the blood stream via the kidney in 2 sheep, 75% being cleared within 8 h. Mean daily urinary oxalate excretions over 5 days were 21-2 and 27-5 mg and the derived plasma oxalate concentrations were 52-6 and 74-4 mug/100 ml, respectively. Oxalate was both filtered and secreted by the renal tubule with oxalate/inulin ratios varying from 1-11 to 1-57 in 6 normal sheep. A large increase in calcium excretion induced by calcium borogluconate infusion over 5 days was accompanied by a small but consistent increase in urinary oxalate excretion relative to calcium. Oxalate in blood was to be found mainly in the plasma, there being a small (8%) proporation within erythrocytes. This is lower than that reported for man, and yet in its excretion of oxalate via the kidney the sheep appears to closely resemble man and dog.

  1. Purfication and properties of a specific isoflavone 7-O-glucoside-6''-malonate malonyestrase from roots of chickpea (Cicer arietinum L.).

    PubMed

    Hinderer, W; Köster, J; Barz, W

    1986-08-01

    Protein extracts from roots of chickpea (Cicer arietinum L.) plants contained high esterase activity hydrolyzing malonate hemiesters of isoflavone 7-O-glucosides. Using 5,7-dihydroxy-4'-methoxyisoflavone (biochanin A) 7-O-glucoside-6"-malonate as a substrate, a specific malonylesterase was purified about 700-fold to near homogeneity. The purified enzyme possesses an extremely low enzyme activity with synthetic esterase substrates. Various putative nonspecific esterases, as tested with alpha-naphthylacetate, were removed during enzyme purification. The malonylesterase demonstrated a very high molecular mass in gel chromatography and in sedimentation analyses with sucrose gradients (greater than or equal to 2 X 10(6)). Analytical sodium dodecyl sulfate-polyacrylamide gel electrophoresis pointed to a single subunit of 32,000. The catalyzed reaction showed a pH optimum at 7.5 and a temperature optimum between 30 and 35 degrees C. The apparent Km for biochanin A 7-O-glucoside-6"-malonate was (4.2 +/- 1.2) X 10(-4) M. The malonylesterase was insensitive to the esterase inhibitors eserine and neostigmine (10(-3) M) as well as phenylmethylsulfonyl fluoride, paraoxon, and diisopropylfluorophosphate (10(-4) M). On the other hand enzyme activity was totally inhibited by Hg2+ ions (10(-5) M) and p-hydroxymercuribenzoate (10(-4) M), whereas iodoacetamide (10(-6)-10(-4) M) inhibited only partially. Di- and tricarboxylic acids strongly stimulated enzyme activity at 10(-2) M. These properties indicate that the malonylesterase from chickpea roots greatly differs from other known esterases. The possible biological function of the specific malonylesterase is discussed in relation to isoflavone conjugate metabolism in chickpea.

  2. The Interaction between Enterobacteriaceae and Calcium Oxalate Deposits

    PubMed Central

    Barr-Beare, Evan; Saxena, Vijay; Hilt, Evann E.; Thomas-White, Krystal; Schober, Megan; Li, Birong; Becknell, Brian; Hains, David S.; Wolfe, Alan J.; Schwaderer, Andrew L.

    2015-01-01

    Background The role of calcium oxalate crystals and deposits in UTI pathogenesis has not been established. The objectives of this study were to identify bacteria present in pediatric urolithiasis and, using in vitro and in vivo models, to determine the relevance of calcium oxalate deposits during experimental pyelonephritis. Methods Pediatric kidney stones and urine were collected and both cultured and sequenced for bacteria. Bacterial adhesion to calcium oxalate was compared. Murine kidney calcium oxalate deposits were induced by intraperitoneal glyoxalate injection and kidneys were transurethrally inoculated with uropathogenic Escherichia coli to induce pyelonephritis Results E. coli of the family Enterobacteriaceae was identified in patients by calcium oxalate stone culture. Additionally Enterobacteriaceae DNA was sequenced from multiple calcium oxalate kidney stones. E. coli selectively aggregated on and around calcium oxalate monohydrate crystals. Mice inoculated with glyoxalate and uropathogenic E. coli had higher bacterial burdens, increased kidney calcium oxalate deposits and an increased kidney innate immune response compared to mice with only calcium oxalate deposits or only pyelonephritis. Conclusions In a murine model, the presence of calcium oxalate deposits increases pyelonephritis risk, likely due to preferential aggregation of bacteria on and around calcium oxalate crystals. When both calcium oxalate deposits and uropathogenic bacteria were present, calcium oxalate deposit number increased along with renal gene transcription of inner stone core matrix proteins increased. Therefore renal calcium oxalate deposits may be a modifiable risk factor for infections of the kidney and urinary tract. Furthermore, bacteria may be present in calcium oxalate deposits and potentially contribute to calcium oxalate renal disease. PMID:26448465

  3. Determining the Biochemical Properties of the Oxalate Biosynthetic Component (Obc)1 from Burkholderia mallei

    PubMed Central

    Lambert, Peter M.

    2016-01-01

    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 quorum sensing dependent and to support pathogenicity and cell viability. In light of the critical roles of oxalate in Burkholderia as well as other organisms, it is surprising that our understanding of how this simple dicarboxylate is biosynthesized remains incomplete. Here we report the expression, purification, and partial characterization of the first intact bacterial oxalate biosynthetic enzyme, Obc1, from B. mallei. An N-terminal His-tagged Bmobc1 was cloned into pDUET, expressed in E. coli BLR (DE3), and the recombinant enzyme purified by affinity chromatography. Oxalate biosynthetic enzyme assays coupled with HPLC analysis revealed that BmObc1 catalyzed the biosynthesis of oxalate, acetoacetate, and free CoA from oxaloacetate and a short chain acyl-CoA following Michaelis-Menten kinetics. Optimal enzyme activity was measured at pH 8.0 and a temperature around 44°C. Kinetic analysis conducted under conditions of saturating acetyl-CoA and varying oxaloacetate concentrations resulted in a calculated Km value for oxaloacetate of 94.3± 9.2 μM (mean ± SE). Under conditions of saturating oxaloacetate concentration and varying acyl-CoA (acetyl- or propionyl-CoA) concentrations kinetic analysis generated a calculated Km value of 26.8 ± 2.3 μM (mean ± SE) for acetyl-CoA and 104.4 ± 12.7 μM for propionyl-CoA. The significantly lower Km for acetyl-CoA suggests that it is strongly favored as a substrate over propionyl-CoA. PMID:27643499

  4. Determining the Biochemical Properties of the Oxalate Biosynthetic Component (Obc)1 from Burkholderia mallei.

    PubMed

    Lambert, Peter M; Nakata, Paul A

    2016-01-01

    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 quorum sensing dependent and to support pathogenicity and cell viability. In light of the critical roles of oxalate in Burkholderia as well as other organisms, it is surprising that our understanding of how this simple dicarboxylate is biosynthesized remains incomplete. Here we report the expression, purification, and partial characterization of the first intact bacterial oxalate biosynthetic enzyme, Obc1, from B. mallei. An N-terminal His-tagged Bmobc1 was cloned into pDUET, expressed in E. coli BLR (DE3), and the recombinant enzyme purified by affinity chromatography. Oxalate biosynthetic enzyme assays coupled with HPLC analysis revealed that BmObc1 catalyzed the biosynthesis of oxalate, acetoacetate, and free CoA from oxaloacetate and a short chain acyl-CoA following Michaelis-Menten kinetics. Optimal enzyme activity was measured at pH 8.0 and a temperature around 44°C. Kinetic analysis conducted under conditions of saturating acetyl-CoA and varying oxaloacetate concentrations resulted in a calculated Km value for oxaloacetate of 94.3± 9.2 μM (mean ± SE). Under conditions of saturating oxaloacetate concentration and varying acyl-CoA (acetyl- or propionyl-CoA) concentrations kinetic analysis generated a calculated Km value of 26.8 ± 2.3 μM (mean ± SE) for acetyl-CoA and 104.4 ± 12.7 μM for propionyl-CoA. The significantly lower Km for acetyl-CoA suggests that it is strongly favored as a substrate over propionyl-CoA. PMID:27643499

  5. Effects of dietary interventions on 24-hour urine parameters in patients with idiopathic recurrent calcium oxalate stones.

    PubMed

    Kıraç, Mustafa; Küpeli, Bora; Irkilata, Lokman; Gülbahar, Ozlem; Aksakal, Nur; Karaoğlan, Ustünol; Bozkırlı, Ibrahim

    2013-02-01

    The aim of this study is to investigate the effects of dietary factors on 24-hour urine parameters in patients with idiopathic recurrent calcium oxalate stones. A total of 108 of idiopathic recurrent calcium oxalate stones were included in the study. A 24-hour urinalysis was performed and metabolic abnormalities were measured for all of the patients. All of the patients were given specialized diets for their 24-hour urine abnormalities. At the end of first month, the same parameters were examined in another 24-hour urinalysis. Hyperoxaluria, hypernatruria, and hypercalciuria were found in 84 (77%), 43 (39.8%), and 38 (35.5%) of the patients, respectively. The differences between the oxalate, sodium, volume, uric acid, and citrate parameters before and after the dietary intervention were significant (p < 0.05). The calcium parameters were not significantly different before and after the intervention. We found that oxalate, sodium, volume, uric acid, and citrate-but not calcium-abnormalities in patients with recurrent calcium oxalate stones can be corrected by diet. The metabolic profiles of idiopathic calcium oxalate stone patients should be evaluated and the appropriate dietary interventions should be implemented to decrease stone recurrence.

  6. Calcium oxalate calculi-induced clusterin expression in kidney.

    PubMed

    Li, Jin-Yi; Liu, Junjiang; Jiang, Junyi; Pumill, Chris; Elaiho, Cordelia; Zhang, Yunxia; Li, Shoubin; Zhou, Tie

    2015-10-01

    The aim of the study was to investigate clusterin expression in the kidney and evaluate the urine clusterin level in the kidney stone formers. (1) In vitro, we treated the Madin-Darby canine kidney (MDCK) cell line with different concentrations of calcium oxalate (CaOx), and then the clusterin protein expression in the cells was evaluated by Western blotting. (2) Kidney stone patients who received percutaneous nephrolithotomy were enrolled in our study. Urine samples were collected before surgery, the kidney punctured to obtain kidney tissue guided by ultrasound intraoperatively. Clusterin expression in the human kidney tissue was evaluated by immunochemistry. The urine clusterin level was determined by enzyme-linked immunosorbent assay. Non-kidney disease subjects were chosen as controls. In vitro, the clusterin expression was up-regulated in the MDCK cells induced by CaOx. The study included 49 patients and 41 non-kidney disease subjects. All calculi were composed of calcium oxalate monohydrate or calcium oxalate dihydrate and a few also contained protein or uric acid. Mean ± SD urine clusterin level was 17.47 ± 18.61 μg/ml in patients, and 3.31 ± 5.42 μg/ml in non-kidney disease subjects, respectively (p < 0.001). Immunohistochemistry revealed the clusterin was located in the cytoplasm of the renal distal and collecting tubular epithelial cells. Also the tissue clusterin expression increased significantly in the kidney stone formers compared to the control groups (p = 0.001). CaOx could induce clusterin expression in renal tubular cells, and increase clusterin levels in the kidney and urine from the kidney stone formers.

  7. Vibrational spectra of the two hydrates of strontium oxalate.

    PubMed

    D'Antonio, Maria C; Torres, María M; Palacios, Daniel; González-Baró, Ana C; Baran, Enrique J

    2015-02-25

    The infrared and Raman spectra of the two hydrates of strontium oxalate, SrC2O4⋅H2O and SrC2O4⋅2H2O, were recorded and discussed on the basis of their structural peculiarities and in comparison with the spectra of the related calcium oxalates and other previously investigated metallic oxalates.

  8. 40 CFR 721.10628 - Mixed metal oxalate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed metal oxalate (generic). 721... Substances § 721.10628 Mixed metal oxalate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxalate (PMN...

  9. 40 CFR 721.10628 - Mixed metal oxalate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed metal oxalate (generic). 721... Substances § 721.10628 Mixed metal oxalate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxalate (PMN...

  10. Acute oxalate nephropathy associated with Clostridium difficile colitis.

    PubMed

    Cohen-Bucay, Abraham; Garimella, Pranav; Ezeokonkwo, Chukwudi; Bijol, Vanesa; Strom, James A; Jaber, Bertrand L

    2014-01-01

    We report the case of a 69-year-old man who presented with acute kidney injury in the setting of community-acquired Clostridium difficile-associated diarrhea and biopsy-proven acute oxalate nephropathy. We discuss potential mechanisms, including increased colonic permeability to oxalate. We conclude that C difficile-associated diarrhea is a potential cause of acute oxalate nephropathy. PMID:24183111

  11. Fabrication of C60 Tri-Diethyl Malonate Membrane via an Electrospinning Method and Its Antibacterial Property.

    PubMed

    Li, Hui; Chen, Shou; Peng, Xiaohua; Sun, Jiangning; Shu, Chunying; Jiang, Li; Wang, Chunru

    2016-03-01

    A homogeneous C60 tri-diethyl malonate membrane was fabricated by a facile electro-spinning method. Comprehensive characterizations of its assembling structure, such as SEM, TEM, TGA, UV-vis, and FTIR, were carried out. Different fullerene derivatives show different assembling characters during the electrospining process. Notably, C60 tri-diethyl malonate with close-knite structures can form a stable structure after removing the assistant polymer of PVP. The antibacterial experiments of C60 tri-diethyl malonate membrane were performed, and the results revealed that this membrane owns excellent antibacterial activity.

  12. Fabrication of C60 Tri-Diethyl Malonate Membrane via an Electrospinning Method and Its Antibacterial Property.

    PubMed

    Li, Hui; Chen, Shou; Peng, Xiaohua; Sun, Jiangning; Shu, Chunying; Jiang, Li; Wang, Chunru

    2016-03-01

    A homogeneous C60 tri-diethyl malonate membrane was fabricated by a facile electro-spinning method. Comprehensive characterizations of its assembling structure, such as SEM, TEM, TGA, UV-vis, and FTIR, were carried out. Different fullerene derivatives show different assembling characters during the electrospining process. Notably, C60 tri-diethyl malonate with close-knite structures can form a stable structure after removing the assistant polymer of PVP. The antibacterial experiments of C60 tri-diethyl malonate membrane were performed, and the results revealed that this membrane owns excellent antibacterial activity. PMID:27455662

  13. Water uptake of internally mixed ammonium sulfate and dicarboxylic acid particles probed by infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Miñambres, Lorena; Méndez, Estíbaliz; Sánchez, María N.; Castaño, Fernando; Basterretxea, Francisco J.

    2013-05-01

    Tropospheric aerosols are usually mixtures of inorganic and organic compounds in variable proportions, and the relative amount of organic fraction can influence the hygroscopic properties of the particles. Infrared spectra of submicrometer internally mixed dry particles of ammonium sulfate (AS) with various dicarboxylic acids (oxalic, malonic, maleic, glutaric and pimelic) have been measured in an aerosol flow tube at several solute mass ratios. The spectra show a notable broadening in the bandwidth of sulfate ion ν3 vibrational band near 1115 cm-1 with respect to pure AS. We attribute these perturbations, that are biggest at AS/organic acid mass ratio near unity, to intermolecular interactions between inorganic ions and organic acid molecules in the internally mixed solids. The water uptake behavior of internally mixed particles has been measured by recording the infrared integrated absorbance of liquid water as a function of relative humidity (RH). The amount of water present in the particles prior to deliquescence correlates partially with the water solubilities of the dicarboxylic acids, and also with the relative magnitudes of intermolecular interactions in the internally mixed dry solids. Phase change of ammonium sulfate in the internally mixed particles with RH has been spectrally monitored, and it is shown that water uptaken before full deliquescence produces structural changes in the particles that are revealed by their vibrational spectra.

  14. Malonate-containing manganese(III) complexes: synthesis, crystal structure, and magnetic properties of AsPh4[Mn(mal)2(H2O)2].

    PubMed

    Delgado, Fernando S; Kerbellec, Nicolas; Ruiz-Pérez, Catalina; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2006-02-01

    The novel manganese(III) complexes PPh4[Mn(mal)2(H2O)2] (1) and AsPh4[Mn(mal)2(H2O)2] (2) (PPh4+ = tetraphenylphosphonium cation, AsPh4+ = tetraphenylarsonium cation, and H2mal = malonic acid) have been prepared, and the structure of 2 was determined by X-ray diffraction analysis. 2 is a mononuclear complex whose structure is made up of trans-diaquabis(malonato)manganate(III) units and tetraphenylarsonium cations. Two crystallographically independent manganese(III) ions (Mn(1) and Mn(2)) occur in 2 that exhibit elongated octahedral surroundings with four oxygen atoms from two bidentate malonate groups in equatorial positions (Mn(1)-O = 1.923(6) and 1.9328(6) A and Mn(2)-O = 1.894(6) and 1.925(6) A) and two trans-coordinated water molecules in the axial sites (Mn(1)-Ow = 2.245(6) A and Mn(2)-Ow = 2.268(6) A). The [Mn(mal)2(H2O)2]- units are linked through hydrogen bonds involving the free malonate-oxygen atoms and the coordinated water molecules to yield a quasi-square-type anionic layer growing in the ab plane. The shortest intralayer metal-metal separations are 7.1557(7) and 7.1526(7) A (through the edges of the square). The anionic sheets are separated from each other by layers of AsPh4+ where sextuple- and double-phenyl embraces occur. The magnetic behavior of 1 and 2 in the temperature range 1.9-290 K reveals the occurrence of weak intralayer ferromagnetic interactions (J = +0.081(1) (1) and +0.072(2) cm(-1) (2)). These values are compared to those of the weak antiferromagnetic coupling [J = -0.19(1) cm(-1)], which is observed in the chain compound K2[Mn(mal)2(MeOH)2][Mn(mal)2] (3), where the exchange pathway involves the carboxyate-malonate bridge in the anti-syn conformation. The structure of 3 was reported elsewhere. Theoretical calculations on fragment models of 2 and 3 were performed to analyze and substantiate both the nature and magnitude of the magnetic couplings observed.

  15. 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

  16. The effect of glycosaminoglycans on the crystallisation of calcium oxalate.

    PubMed

    Kohri, K; Garside, J; Blacklock, N J

    1989-06-01

    The effect of glycosaminoglycans on urinary stone formation was evaluated using a mixed suspension, mixed product removal (MSMPR) crystallisation system together with scanning electron microscopy (SEM) to examine the resulting crystals. Chondroitin sulphate was found to decrease the nucleation rate and to promote both the growth rate and suspension density. Results obtained with hyaluronic acid, although inconclusive, are similar to those given by chondroitin sulphate. Heparin sodium salt had a powerful inhibitory effect on both the nucleation rate and the suspension density, the effect increasing in proportion to the heparin concentration. SEM examination showed that the octahedral habit of calcium oxalate dihydrate was modified by the addition of heparin sodium salt and confirmed that the average crystal size in the presence of chondroitin sulphate and hyaluronic acid was significantly greater than the control or that found in the presence of heparin sodium salt. PMID:2502299

  17. Calcium oxalate nephrolithiasis and tubular necrosis in recent metamorphs of Rana sylvatica (Lithobates sylvaticus) fed spinach during the premetamorphic (tadpole) stage.

    PubMed

    Forzán, M J; Ferguson, L V; Smith, T G

    2015-03-01

    Amphibians in the family Ranidae (true frogs) seem highly susceptible to oxalosis, particularly when fed a diet high in oxalic acid during the premetamorphic (tadpole) stage. The authors describe the mortality of 150 captive-raised wood frogs (Rana sylvatica or Lithobates sylvaticus) from oxalate nephrolithiasis and renal tubular necrosis caused by consumption of boiled spinach during tadpole development. Renal lesions were due to intraluminal transparent crystals which were birefringent under polarized light and were identified morphologically and histochemically as composed of calcium oxalate. Evidence of early fibrosis or squamous metaplasia, and a presentation at least 2 weeks after spinach consumption had ended, suggested a subacute course. Tadpole-feeding protocols should avoid plants with high oxalate content (eg, spinach and rhubarb leaves), and any episode of high mortality in captive amphibians along with nephrolithiasis should prompt an evaluation of the feed sources for material with high oxalate content.

  18. Acute oxalate nephropathy associated with orlistat

    PubMed Central

    Humayun, Youshay; Ball, Kenneth C.; Lewin, Jack R.; Lerant, Anna A.; Fülöp, Tibor

    2016-01-01

    Background: Obesity is a major world-wide epidemic which has led to a surge of various weight loss-inducing medical or surgical treatments. Orlistat is a gastrointestinal lipase inhibitor used as an adjunct treatment of obesity and type 2 diabetes mellitus to induce clinically significant weight loss via fat malabsorption. Case Presentation: We describe a case of a 76-year-old female with past medical history of chronic kidney disease (baseline serum creatinine was 1.5-2.5 mg/dL), hypertension, gout and psoriatic arthritis, who was admitted for evaluation of elevated creatinine, peaking at 5.40 mg/dL. She was started on orlistat 120 mg three times a day six weeks earlier. Initial serologic work-up remained unremarkable. Percutaneous kidney biopsy revealed massive calcium oxalate crystal depositions with acute tubular necrosis and interstitial inflammation. Serum oxalate level returned elevated at 45 mm/l (normal <27). Timed 24-hour urine collection documented increased oxalate excretion repeatedly (54-96 mg/24 hour). After five renal dialysis sessions in eighth days she gradually regained her former baseline kidney function with creatinine around 2 mg/dL. Given coexisting proton-pump inhibitor therapy, only per os calcium-citrate provided effective intestinal oxalate chelation to control hyperoxaluria. Conclusions: Our case underscores the potential of medically induced fat malabsorption to lead to an excessive oxalate absorption and acute kidney injury (AKI), especially in subjects with pre-existing renal impairment. Further, it emphasizes the importance of kidney biopsy to facilitate early diagnosis and treatment. PMID:27152294

  19. Dietary hyperoxaluria is not reduced by treatment with lactic acid bacteria

    PubMed Central

    2013-01-01

    Background Secondary hyperoxaluria either based on increased intestinal absorption of oxalate (enteric), or high oxalate intake (dietary), is a major risk factor of calcium oxalate urolithiasis. Oxalate-degrading bacteria might have beneficial effects on urinary oxalate excretion resulting from decreased intestinal oxalate concentration and absorption. Methods Twenty healthy subjects were studied initially while consuming a diet normal in oxalate. Study participants were then placed on a controlled oxalate-rich diet for a period of 6 weeks. Starting with week 2 of the oxalate-rich diet, participants received 2.6 g/day of a lactic acid bacteria preparation for 5 weeks. Finally, subjects were examined 4 weeks after treatment while consuming again a normal-oxalate diet. Participants provided weekly 24-hour urine specimens. Analyses of blood samples were performed before and at the end of treatment. Results Urinary oxalate excretion increased significantly from 0.354 ± 0.097 at baseline to 0.542 ± 0.163 mmol/24 h under the oxalate-rich diet and remained elevated until the end of treatment, as did relative supersaturation of calcium oxalate. Plasma oxalate concentration was significantly higher after 5 weeks of treatment compared to baseline. Four weeks after treatment, urinary oxalate excretion and relative supersaturation of calcium oxalate fell to reach initial values. Conclusions Persistent dietary hyperoxaluria and increased plasma oxalate concentration can already be induced in healthy subjects without disorders of oxalate metabolism. The study preparation neither reduced urinary oxalate excretion nor plasma oxalate concentration. The preparation may be altered to select for lactic acid bacteria strains with the highest oxalate-degrading activity. PMID:24330782

  20. Calcium Oxalate Crystals in Eucalypt Ectomycorrhizae: Morphochemical Characterization

    PubMed Central

    Pylro, Victor Satler; de Freitas, André Luiz Moreira; Otoni, Wagner Campos; da Silva, Ivo Ribeiro; Borges, Arnaldo Chaer; Costa, Maurício Dutra

    2013-01-01

    Ectomycorrhizal fungi are ubiquitous in forest ecosystems, benefitting plants principally by increasing the uptake of water and nutrients such as calcium from the soil. Previous work has demonstrated accumulation of crystallites in eucalypt ectomycorrhizas, but detailed morphological and chemical characterization of these crystals has not been performed. In this work, cross sections of acetic acid-treated and cleared ectomycorrhizal fragments were visualized by polarized light microscopy to evaluate the location of crystals within cortical root cells. Ectomycorrhizal sections were also observed by scanning electron microscopy (SEM) coupled with energy dispersive x-ray (EDS) microprobe analysis. The predominant forms of crystals were crystal sand (granules) and concretions. Calcium, carbon and oxygen were detected by EDS as constituent elements and similar elemental profiles were observed between both crystal morphologies. All analyzed crystalline structures were characterized as calcium oxalate crystals. This is the first report of the stoichiometry and morphology of crystals occurring in eucalypt ectomycorrhizas in tropical soils. The data corroborates the role of ectomycorrhizae in the uptake and accumulation of calcium in the form of calcium oxalate crystals in hybrid eucalypt plants. PMID:23844062

  1. Growth and characterization of an organic nonlinear optical material: L-Histidine malonate

    NASA Astrophysics Data System (ADS)

    Ramya, K.; Saraswathi, N. T.; Raja, C. Ramachandra

    2016-10-01

    L-Histidine malonate is one of the potential organic material for nonlinear optical applications. Single crystals of L-Histidine malonate were grown by the liquid diffusion method. The lattice parameter values were evaluated from single crystal X-ray diffraction technique. The Fourier Transform Infra Red and Raman spectral studies were employed to identify the different modes of vibrations of molecular groups in the crystal. Optical characterization and the percentage of optical transmission were recorded using UV-vis-NIR spectroscopy. The molecular structure was established by proton and carbon Nuclear magnetic resonance spectral studies. The thermal behavior of the material has been studied by Thermo gravimetric and Differential thermal plots. The second harmonic generation conversion efficiency was found out from the powder technique of Kurtz and Perry.

  2. Oxalate transport by anion exchange across rabbit ileal brush border.

    PubMed Central

    Knickelbein, R G; Aronson, P S; Dobbins, J W

    1986-01-01

    This study demonstrates the presence of oxalate transporters on the brush border membrane of rabbit ileum. We found that an inside alkaline (pH = 8.5 inside, 6.5 outside) pH gradient stimulated [14C]oxalate uptake 10-fold at 1 min with a fourfold accumulation above equilibrated uptake at 5 min. 1 mM 4,4'-diisothiocyanostilbene-2,2'-disulfonate (disodium salt; DIDS) profoundly inhibited the pH-gradient stimulated oxalate uptake. Using an inwardly directed K+ gradient and valinomycin, we found no evidence for potential sensitive oxalate uptake. In contrast to Cl:HCO3 exchange, HCO3 did not stimulate oxalate uptake more than was seen with a pH gradient in the absence of HCO3. An outwardly directed Cl gradient (50 mM inside, 5 mM outside) stimulated oxalate uptake 10-fold at 1 min with a fivefold accumulation above equilibrated uptake. Cl-stimulated oxalate uptake was largely inhibited by DIDS. Addition of K+ and nigericin only slightly decreased the Cl gradient-stimulated oxalate uptake, which indicates that this stimulation was not primarily due to the Cl gradient generating an inside alkaline pH gradient via Cl:OH exchange. Further, an outwardly directed oxalate gradient stimulated 36Cl uptake. These results suggested that both oxalate:OH and oxalate:Cl exchange occur on the brush border membrane. To determine if one or both of these exchanges were on contaminating basolateral membrane, the vesicle preparation was further fractionated into a brush border and basolateral component using sucrose density gradient centrifugation. Both exchangers localized to the brush border component. A number of organic anions were examined (outwardly directed gradient) to determine if they could stimulate oxalate and Cl uptake. Only formate and oxaloacetate were found to stimulate oxalate and Cl uptake. An inwardly directed Na gradient only slightly stimulated oxalate uptake, which was inhibited by DIDS. PMID:3003149

  3. Production of calcium oxalate crystals by the basidiomycete Moniliophthora perniciosa, the causal agent of witches' broom disease of Cacao.

    PubMed

    Rio, Maria Carolina S do; de Oliveira, Bruno V; de Tomazella, Daniela P T; Silva, José A Fracassi da; Pereira, Gonçalo A G

    2008-04-01

    Oxalic acid has been shown as a virulence factor for some phytopathogenic fungi, removing calcium from pectin and favoring plant cell wall degradation. Recently, it was published that calcium oxalate accumulates in infected cacao tissues during the progression of Witches' Broom disease (WBD). In the present work we report that the hemibiotrophic basidiomycete Moniliophthora perniciosa, the causal agent of WBD, produces calcium oxalate crystals. These crystals were initially observed by polarized light microscopy of hyphae growing on a glass slide, apparently being secreted from the cells. The analysis was refined by Scanning electron microscopy and the compositon of the crystals was confirmed by energy-dispersive x-ray spectrometry. The production of oxalate by M. perniciosa was reinforced by the identification of a putative gene coding for oxaloacetate acetylhydrolase, which catalyzes the hydrolysis of oxaloacetate to oxalate and acetate. This gene was shown to be expressed in the biotrophic-like mycelia, which in planta occupy the intercellular middle-lamella space, a region filled with pectin. Taken together, our results suggest that oxalate production by M. perniciosa may play a role in the WBD pathogenesis mechanism.

  4. Organocatalytic asymmetric addition of malonates to unsaturated 1,4-diketones

    PubMed Central

    Žari, Sergei; Kailas, Tiiu; Kudrjashova, Marina; Öeren, Mario; Järving, Ivar; Tamm, Toomas; Lopp, Margus

    2012-01-01

    Summary The organocatalytic Michael addition of malonates to symmetric unsaturated 1,4-diketones catalyzed by thiourea and squaramide derivatives with Cinchona alkaloids afforded the formation of a new C–C bond in high yields (up to 98%) and enantiomeric purities (up to 93%). The absolute configuration of the product was suggested from comparison of the experimental and calculated VCD spectra of the reaction product 3a. PMID:23019480

  5. Phosphine-catalyzed asymmetric additions of malonate esters to γ-substituted allenoates and allenamides

    PubMed Central

    Sinisi, Riccardo; Sun, Jianwei; Fu, Gregory C.

    2010-01-01

    Because carbonyl groups are ubiquitous in organic chemistry, the ability to synthesize functionalized carbonyl compounds, particularly enantioselectively, is an important objective. We have developed a straightforward and versatile method for catalytic asymmetric carbon–carbon bond formation at the γ-position of carbonyl compounds, specifically, phosphine-catalyzed additions of malonate esters to γ-substituted allenoates and allenamides. Mechanistic studies have provided insight into the reaction pathway. PMID:20624987

  6. Malonate induces cell death via mitochondrial potential collapse and delayed swelling through an ROS-dependent pathway

    PubMed Central

    Fernandez-Gomez, Francisco J; Galindo, Maria F; Gómez-Lázaro, Maria; Yuste, Victor J; Comella, Joan X; Aguirre, Norberto; Jordán, Joaquín

    2005-01-01

    Herein we study the effects of the mitochondrial complex II inhibitor malonate on its primary target, the mitochondrion. Malonate induces mitochondrial potential collapse, mitochondrial swelling, cytochrome c (Cyt c) release and depletes glutathione (GSH) and nicotinamide adenine dinucleotide coenzyme (NAD(P)H) stores in brain-isolated mitochondria. Although, mitochondrial potential collapse was almost immediate after malonate addition, mitochondrial swelling was not evident before 15 min of drug presence. This latter effect was blocked by cyclosporin A (CSA), Ruthenium Red (RR), magnesium, catalase, GSH and vitamin E. Malonate added to SH-SY5Y cell cultures produced a marked loss of cell viability together with the release of Cyt c and depletion of GSH and NAD(P)H concentrations. All these effects were not apparent in SH-SY5Y cells overexpressing Bcl-xL. When GSH concentrations were lowered with buthionine sulphoximine, cytoprotection afforded by Bcl-xL overexpression was not evident anymore. Taken together, all these data suggest that malonate causes a rapid mitochondrial potential collapse and reactive oxygen species production that overwhelms mitochondrial antioxidant capacity and leads to mitochondrial swelling. Further permeability transition pore opening and the subsequent release of proapoptotic factors such as Cyt c could therefore be, at least in part, responsible for malonate-induced toxicity. PMID:15655518

  7. Self-assembly in solvates of 2,4-diamino-6-(4-methyl- phenyl)-1,3,5-triazine and in its molecular adducts with some aliphatic dicarboxylic acids

    NASA Astrophysics Data System (ADS)

    Nandy, Purnendu; Nayak, Amrita; Biswas, Sharmita Nandy; Pedireddi, V. R.

    2016-03-01

    Solid state structures of 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 1, in the form of methanol and dimethylsulfoxide (DMSO) solvates, as well as supramolecular assemblies of 1 with various aliphatic dicarboxylic acids, oxalic (a), malonic (b), succinic (c), glutaric (d) and adipic (e) have been reported. Analysis of the assemblies has been carried out by single crystal X-ray diffraction and thermal methods. Triazine 1 yields anhydrous molecular adducts with acids a-d, upon co-crystallization either from CH3OH and DMSO solvents. However acid e gives anhydrous adduct from DMSO solvent, while it gives a methanol adduct from CH3OH. Structure determination reveals that molecular adducts 1a, 1d and 1e are in a 2:1 ratio of 1 and the corresponding acid. However the ratio is 1:1, in 1b, perhaps due to the involvement of one of the acid groups in the intramolecular hydrogen bonding and in adduct 1c the ratio observed is 3:2. Structural features in all these assemblies have been rationalised in terms of various recognition patterns formed between the acceptor and donor groups. A noteworthy feature is that -COOH groups in acid a establish interaction with 1 through amino groups, while such interactions are observed to be through hetero -N atoms in case of the acids b-e.

  8. Exudation of organic acids by a marsh plant and implications on trace metal availability in the rhizosphere of estuarine sediments

    NASA Astrophysics Data System (ADS)

    Mucha, Ana P.; Almeida, C. Marisa R.; Bordalo, Adriano A.; Vasconcelos, M. Teresa S. D.

    2005-10-01

    The aim of this work was to identify a variety of low molecular weight organic acids exuded by the sea rush Juncus maritimus collected at two locations with different sediment characteristics (sandy and muddy) and to examine whether specific differences in physico-chemical sediment characteristics influenced plant exudation. Just after collection, plant roots were rinsed and put in contact with deionised water for 2 h. In the obtained solution the organic acids, exuded by the plants, were determined by high performance liquid chromatography. Juncus maritimus was shown to be capable of releasing malonate and oxalate. Sediments and rhizosediments (sediment in contact with the plant roots and rhizomes, corresponding to the area of higher belowground biomass) from the areas where the plants had been collected were characterised in terms of physical and chemical composition, including acid volatile sulphide and total-recoverable metals (Pb, Cr, Cu, Zn, Ni and Cd). It was found that the extent of exudation varied markedly between sites. The identified organic acids were used as extractants of metals from sediments and rhizosediments and the results were compared with those provided by a very commonly used sequential extraction approach, which was carried out in parallel. This work demonstrates that J. maritimus can release organic compounds that can act as complexing agents of trace metal and therefore organic exudates should be accounted for when dealing with estuarine environment quality.

  9. The Effect of Methyl, Hydroxyl, and Ketone Functional Groups on the Heterogeneous Oxidation of Succinic Acid Aerosol by OH Radicals

    NASA Astrophysics Data System (ADS)

    Chan, M.; Zhang, H.; Wilson, K. R.

    2013-12-01

    The heterogeneous oxidation of atmospheric organic aerosols can influence their effects on climate, human health, and visibility. During oxidation, functionalization occurs when an oxygenated functional group is added to a molecule, leaving the carbon skeleton intact. Fragmentation involves carbon-carbon bond cleavage and produces two products with smaller carbon numbers than the parent compound. To gain better insights into how the molecular structure of more oxygenated organic compounds affects heterogeneous reactivity, succinic acid aerosols are photo-oxidized in an aerosol flow tube reactor, and the reaction products are analyzed using Direct Analysis in Real Time Mass Spectrometry for online chemical analysis. The effect of various functional groups (CH3, OH, C=O) along the carbon backbone on the heterogeneous reaction mechanisms are also investigated using model compounds. For this series of compounds, the formation of more oxygenated products through functionalization can be explained by well-known condensation-phase reactions such as Russell and Bennett and Summers. The number of fragmentation products is found to increase with the presence of OH and CH3 groups. This can be attributed to the increased number of tertiary carbons, enhancing the fragmentation after multiple oxidation steps. Smaller dicaids (oxalic acid and malonic acid) can be formed through the fragmentation processes in the heterogeneous oxidation of succinic acid. The effect of molecular structure on reaction kinetics, volatilization, and the relative importance of functionalization and fragmentation pathways will be discussed.

  10. Oxalate nephropathy due to gastrointestinal disorders.

    PubMed Central

    Canos, H J; Hogg, G A; Jeffery, J R

    1981-01-01

    Renal failure secondary to oxalate interstitial nephritis developed in three patients with malabsorption and steatorrhea following a jejunoileal bypass, extensive small intestine resection and a partial gastrectomy. Hyperoxaluria was documented in two of the cases. The possibility that this complication can occur in patients after a jejunoileal bypass operation is now recognized. This report shows that it can also occur in patients with other bowel disorders that cause malabsorption and steatorrhea. Since the prognosis for patients with oxalate nephropathy is poor, renal function should be closely monitored in patients who are at risk because of these disorders. Therapy should be directed at correcting malabsorption, steatorrhea and hyperoxaluria. When the renal function of patients with a jejunoileal bypass continues to decline despite intensive medical therapy, restoration of bowel continuity is strongly recommended. Images FIG. 1 FIG. 2 FIG. 3 PMID:7471017

  11. Crystal growth of calcium oxalate monohydrate

    NASA Astrophysics Data System (ADS)

    Singh, R. P.; Gaur, S. S.; Sheehan, M. E.; Nancollas, G. H.

    1988-02-01

    The kinetics of crystal growth of calcium oxalate monohydrate has been investigated up to very large extents of growth over a range of supersaturations maintained using the Constant Composition technique. It is suggested that the initial rapid growth of aged seed crystals resulting in marked lattice perfection, reduces the density of growth sites on the crystal surfaces. A method for the preparation of perfected crystallites of calcium oxalate monohydrate through pregrowth of aged crystals has been developed. At large extents of growth with respect to initial seed crystals ( > 200% for aged crystals and 30-60% for pregrown crystals), the rates of crystallization at constant supersaturation undergo marked increases accompanying the formulation of secondary nuclei. These nucleation thresholds depend both upon supersaturation and upon the initial specific surface area of the crystallites and may be important factors in the formation of calcium oxalate stones in vivo. Experiments in whole urine suggest that the kinetics of growth, secondary nucleation, aggregation and cementation of particles may be important factors in kidney stone formation.

  12. Mixed ligand complexes of Cu(II)-2-(2-pyridyl)-benzimidazole and aliphatic or aromatic dicarboxylic acids: Synthesis, characterization and biological activity

    NASA Astrophysics Data System (ADS)

    El-Sherif, Ahmed A.; Jeragh, Bakir J. A.

    2007-11-01

    The synthesis and structural characterization of mixed ligand complexes derived from 2-(2-pyridyl)-benzimidazole (PBI) (1ry ligand) and aliphatic or aromatic dicarboxylic acids (2ry ligand) are reported. Cu(II) complexes were characterized on the bases of their elemental analyses, IR, ESR and thermal analyses. The elemental analysis indicated the formation of mixed ligand complexes in a mole ratio 1:1:1 (Cu:L 1:L 2), L 1 = PBI and L 2 = oxalic acid, phthalic acid or malonic acid. IR spectra showed that PBI acts as a neutral bidentate coordinated to the Cu(II) via the pyridyl and imidazolyl nitrogen atoms. The dicarboxylic acids are bidentate with monodentate carboxylate groups. Thermal decomposition study of complexes was monitored by thermogravimetric (TG) and derivative thermogravimetric (DTG) analysis in N 2 atmosphere. The decomposition course and steps were analysed and the activation parameters of the nonisothermal decomposition were calculated from the TG curves and discussed. The isolated metal chelates were screened for their antimicrobial activities and the results are reported, discussed and compared with some known antibiotics.

  13. Synthesis and spectroscopic characterization of magnesium oxalate nano-crystals.

    PubMed

    Lakshmi Reddy, S; Ravindra Reddy, T; Siva Reddy, G; Endo, Tamio; Frost, Ray L

    2014-04-01

    Synthesis of MgC92)O(4)⋅2H(2)O nano particles was carried out by thermal double decomposition of solutions of oxalic acid dihydrate (C(2)H(2)O(4)⋅2H(2)O) and Mg(OAc)(2)⋅(40H(2)O employing CATA-2R microwave reactor. Structural elucidation was carried out by employing X-ray diffraction (XRD), particle size and shape were studied by transmission electron microscopy (TEM) and nature of bonding was investigated by optical absorption and near-infrared (NIR) spectral studies. The powder resulting from this method is pure and possesses distorted rhombic octahedral structure. The synthesized nano rod is 80 nm in diameter and 549 nm in length.

  14. Protein adsorption at calcium oxalate monohydrate crystal surfaces.

    NASA Astrophysics Data System (ADS)

    Wesson, J.; Sheng, X.; Rimer, J.; Jung, T.; Ward, M.

    2008-03-01

    Calcium oxalate monohydrate (COM) crystals are the dominant inorganic phase in most kidney stones, and kidney stones form as aggregates of COM crystals and organic material, principally proteins, but little is known about the molecular level events at COM surfaces that regulate COM aggregation. We have examined the influence of polyelectrolytes on the force of adhesion between chemically modified atomic force microscopy (AFM) tips and selected COM crystal faces in saturated solution. In general, we found that polyanions bind to COM surfaces and block adhesion of a carboxylate functionalized AFM tip, while polycations had no measureable effect on adhesion force under the same conditions. We did observe a unique absence of interaction between poly(glutamic acid) and the COM (100) face compared to other synthetic polyanions, and some native urinary protein structures also exhibited unique face selective interactions, suggesting that simple electrostatic models will not completely explain the data.

  15. Sources and atmospheric processes impacting oxalate at a suburban coastal site in Hong Kong: Insights inferred from 1 year hourly measurements

    NASA Astrophysics Data System (ADS)

    Zhou, Yang; Huang, Xiaohui Hilda; Bian, Qijing; Griffith, Stephen M.; Louie, Peter K. K.; Yu, Jian Zhen

    2015-09-01

    Oxalic acid is one of the most abundant dicarboxylic acids in the atmosphere, receiving a great deal of attention due to its potential influence on cloud condensation nucleus activities. In this work, we report 10 months of hourly oxalate measurements in particulate matter of less than 2.5 µm in aerodynamic diameter (PM2.5) by a Monitor for Aerosols and Gases in ambient Air at a suburban coastal site in Hong Kong from April 2012 to February 2013. A total of more than 6000 sets of oxalate and inorganic ion data were obtained. The mean (±SD) oxalate concentration was 0.34 (±0.18) µg m-3, accounting for 2.8% of the total ion mass and 1.5% of the PM2.5 mass. Seasonal variation showed higher concentrations in fall and winter (0.54 and 0.36 µg m-3, respectively) and lower concentrations in spring and summer (~0.26 µg m-3). Different from the inorganic ions, a shallow dip in the oxalate concentration consistently occurred in the morning after sunrise (around 9:00 A.M.) throughout all seasons. Our analysis suggests that this was likely due to photolysis of oxalate-Fe (III) complex under sunlight. In summer, a small daytime peak was discernable for oxalate and nitrate. This characteristic, together with a more evident diurnal variation of O3, indicates comparatively more active photochemical oxidation in summer than other seasons. High correlations were observed between oxalate and non-sea-salt SO42- (NSS) (R2 = 0.63) and Ox (O3 + NO2) (R2 = 0.48), indicating significant commonality in their secondary formation. Positive matrix factorization analysis of oxalate and other real-time gas and particle-phase component data estimates that secondary formation processes, including secondary gas or aqueous oxidation processes (49%), oxidation processes of biomass burning emissions (37%), accounted for the majority of PM2.5 oxalate. A backward trajectories cluster analysis found that higher oxalate/NSS ratios were associated with low pollution samples under the influence of

  16. Evidence that serum calcium oxalate supersaturation is a consequence of oxalate retention in patients with chronic renal failure.

    PubMed Central

    Worcester, E M; Nakagawa, Y; Bushinsky, D A; Coe, F L

    1986-01-01

    Serum oxalate rises in uremia because of decreased renal clearance, and crystals of calcium oxalate occur in the tissues of uremic patients. Crystal formation suggests that either uremic serum is supersaturated with calcium oxalate, or local oxalate production or accumulation causes regional supersaturation. To test the first alternative, we ultrafiltered uremic serum and measured supersaturation with two different methods previously used to study supersaturation in urine. First, the relative saturation ratio (RSR), the ratio of the dissolved calcium oxalate complex to the thermodynamic calcium oxalate solubility product, was estimated for 11 uremic (before and after dialysis) and 4 normal serum samples using a computer program. Mean ultrafiltrate oxalate predialysis was 89 +/- 8 microM/liter (+/- SEM), 31 +/- 4 postdialysis, and 10 +/- 3 in normals. Mean RSR was 1.7 +/- 0.1 (predialysis), 0.7 +/- 0.1 (postdialysis), and 0.2 +/- 0.1 (normal), where values greater than 1 denote supersaturation, less than 1, undersaturation. Second, the concentration product ratio (CPR), the ratio of the measured calcium oxalate concentration product before to that after incubation of the sample with calcium oxalate monohydrate crystal, was measured in seven uremic and seven normal serum ultrafiltrates. Mean oxalate was 91 +/- 11 (uremic) and 8 +/- 3 (normal). Mean CPR was 1.4 +/- 0.2 (uremic) and 0.2 +/- 0.1 (normal). Predialysis, 17 of 18 uremic ultrafiltrates were supersaturated with respect to calcium oxalate. The degree of supersaturation was correlated with ultrafiltrate oxalate (RSR, r = 0.99, r = 29, P less than 0.001; CPR, r = 0.75, n = 11, P less than 0.001). A value of ultrafiltrate oxalate of 50 microM/liter separated undersaturated from supersaturated samples and occurred at a creatinine of approximately 9.0 mg/dl. PMID:3711339

  17. Alarm Photosynthesis: Calcium Oxalate Crystals as an Internal CO2 Source in Plants.

    PubMed

    Tooulakou, Georgia; Giannopoulos, Andreas; Nikolopoulos, Dimosthenis; Bresta, Panagiota; Dotsika, Elissavet; Orkoula, Malvina G; Kontoyannis, Christos G; Fasseas, Costas; Liakopoulos, Georgios; Klapa, Maria I; Karabourniotis, George

    2016-08-01

    Calcium oxalate crystals are widespread among animals and plants. In land plants, crystals often reach high amounts, up to 80% of dry biomass. They are formed within specific cells, and their accumulation constitutes a normal activity rather than a pathological symptom, as occurs in animals. Despite their ubiquity, our knowledge on the formation and the possible role(s) of these crystals remains limited. We show that the mesophyll crystals of pigweed (Amaranthus hybridus) exhibit diurnal volume changes with a gradual decrease during daytime and a total recovery during the night. Moreover, stable carbon isotope composition indicated that crystals are of nonatmospheric origin. Stomatal closure (under drought conditions or exogenous application of abscisic acid) was accompanied by crystal decomposition and by increased activity of oxalate oxidase that converts oxalate into CO2 Similar results were also observed under drought stress in Dianthus chinensis, Pelargonium peltatum, and Portulacaria afra Moreover, in A. hybridus, despite closed stomata, the leaf metabolic profiles combined with chlorophyll fluorescence measurements indicated active photosynthetic metabolism. In combination, calcium oxalate crystals in leaves can act as a biochemical reservoir that collects nonatmospheric carbon, mainly during the night. During the day, crystal degradation provides subsidiary carbon for photosynthetic assimilation, especially under drought conditions. This new photosynthetic path, with the suggested name "alarm photosynthesis," seems to provide a number of adaptive advantages, such as water economy, limitation of carbon losses to the atmosphere, and a lower risk of photoinhibition, roles that justify its vast presence in plants. PMID:27261065

  18. Alarm Photosynthesis: Calcium Oxalate Crystals as an Internal CO2 Source in Plants.

    PubMed

    Tooulakou, Georgia; Giannopoulos, Andreas; Nikolopoulos, Dimosthenis; Bresta, Panagiota; Dotsika, Elissavet; Orkoula, Malvina G; Kontoyannis, Christos G; Fasseas, Costas; Liakopoulos, Georgios; Klapa, Maria I; Karabourniotis, George

    2016-08-01

    Calcium oxalate crystals are widespread among animals and plants. In land plants, crystals often reach high amounts, up to 80% of dry biomass. They are formed within specific cells, and their accumulation constitutes a normal activity rather than a pathological symptom, as occurs in animals. Despite their ubiquity, our knowledge on the formation and the possible role(s) of these crystals remains limited. We show that the mesophyll crystals of pigweed (Amaranthus hybridus) exhibit diurnal volume changes with a gradual decrease during daytime and a total recovery during the night. Moreover, stable carbon isotope composition indicated that crystals are of nonatmospheric origin. Stomatal closure (under drought conditions or exogenous application of abscisic acid) was accompanied by crystal decomposition and by increased activity of oxalate oxidase that converts oxalate into CO2 Similar results were also observed under drought stress in Dianthus chinensis, Pelargonium peltatum, and Portulacaria afra Moreover, in A. hybridus, despite closed stomata, the leaf metabolic profiles combined with chlorophyll fluorescence measurements indicated active photosynthetic metabolism. In combination, calcium oxalate crystals in leaves can act as a biochemical reservoir that collects nonatmospheric carbon, mainly during the night. During the day, crystal degradation provides subsidiary carbon for photosynthetic assimilation, especially under drought conditions. This new photosynthetic path, with the suggested name "alarm photosynthesis," seems to provide a number of adaptive advantages, such as water economy, limitation of carbon losses to the atmosphere, and a lower risk of photoinhibition, roles that justify its vast presence in plants.

  19. Mineralization of flumequine in acidic medium by electro-Fenton and photoelectro-Fenton processes.

    PubMed

    Garcia-Segura, Sergi; Garrido, José A; Rodríguez, Rosa M; Cabot, Pere L; Centellas, Francesc; Arias, Conchita; Brillas, Enric

    2012-05-01

    The mineralization of flumequine, an antimicrobial agent belonging to the first generation of synthetic fluoroquinolones which is detected in natural waters, has been studied by electrochemical advanced oxidation processes (EAOPs) like electro-Fenton (EF) and photoelectro-Fenton (PEF) with UVA light. The experiments were performed in a cell containing a boron-doped diamond (BDD) anode and an air-diffusion cathode to generate H(2)O(2) at constant current. The Fe(2+) ion added to the medium increased the solubility of the drug by the formation of a complex of intense orange colour and also reacted with electrogenerated H(2)O(2) to form hydroxyl radical from Fenton reaction. Oxidant hydroxyl radicals at the BDD surface were produced from water oxidation. A partial mineralization of flumequine in a solution near to saturation with optimum 2.0mM Fe(2+) at pH 3.0 was achieved by EF. The PEF process was more powerful, giving an almost total mineralization with 94-96% total organic carbon removal. Increasing current accelerated both treatments, but with decreasing mineralization current efficiency. Comparative treatments using a real wastewater matrix led to similar degradation degrees. The kinetics for flumequine decay always followed a pseudo-first-order reaction and its rate constant, similar for both EAOPs, raised with increasing current. Generated carboxylic acids like malonic, formic, oxalic and oxamic acids were quantified by ion-exclusion HPLC. Fe(III)-oxalate and Fe(III)-oxamate complexes were the most persistent by-products under EF conditions and their quicker photolysis by UVA light explains the higher oxidation power of PEF. The release of inorganic ions such as F(-), NO(3)(-) and in lesser extent NH(4)(+) was followed by ionic chromatography. PMID:22348999

  20. Electrochemical synthesis and characterization of zinc oxalate nanoparticles

    SciTech Connect

    Shamsipur, Mojtaba; Roushani, Mahmoud; Pourmortazavi, Seied Mahdi

    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 found 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.

  1. Photo-induced cold vapor generation with low molecular weight alcohol, aldehyde, or carboxylic acid for atomic fluorescence spectrometric determination of mercury.

    PubMed

    Han, Chunfang; Zheng, Chengbin; Wang, Jun; Cheng, Guanglei; Lv, Yi; Hou, Xiandeng

    2007-06-01

    With UV irradiation, Hg(2+) in aqueous solution can be converted into Hg(0) cold vapor by low molecular weight alcohols, aldehydes, or carboxylic acids, e.g., methanol, formaldehyde, acetaldehyde, glycol, 1,2-propanediol, glycerol, acetic acid, oxalic acid, or malonic acid. It was found that the presence of nano-TiO(2) more or less improved the efficiency of the photo-induced chemical/cold vapor generation (photo-CVG) with most of the organic reductants. The nano-TiO(2)-enhanced photo-CVG systems can be coupled to various analytical atomic spectrometric techniques for the determination of ultratrace mercury. In this work, we evaluated the application of this method to the atomic fluorescence spectrometric (AFS) determination of mercury in cold vapor mode. Under the optimized experimental conditions, the instrumental limits of detection (based on three times the standard deviation of 11 measurements of a blank solution) were around 0.02-0.04 microg L(-1), with linear dynamic ranges up to 15 microg L(-1). The interference of transition metals and the mechanism of the photo-CVG are briefly discussed. Real sample analysis using the photo-CVG-AFS method revealed that it was promising for water and geological analysis of ultralow levels of mercury.

  2. Malonate-based inhibitors of mammalian serine racemase: kinetic characterization and structure-based computational study.

    PubMed

    Vorlová, Barbora; Nachtigallová, Dana; Jirásková-Vaníčková, Jana; Ajani, Haresh; Jansa, Petr; Rezáč, Jan; Fanfrlík, Jindřich; Otyepka, Michal; Hobza, Pavel; Konvalinka, Jan; Lepšík, Martin

    2015-01-01

    Overactivation of NMDA receptors has been implicated in various neuropathological conditions, including brain ischaemia, neurodegenerative disorders and epilepsy. Production of d-serine, an NMDA receptor co-agonist, from l-serine is catalyzed in vivo by the pyridoxal-5'-phosphate (PLP)-dependent enzyme serine racemase. Specific inhibition of this enzyme has been proposed as a promising strategy for treatment of neurological conditions caused by NMDA receptor dysfunction. Here we present the synthesis and activity analysis of a series of malonate-based inhibitors of mouse serine racemase (mSR). The compounds possessed IC50 values ranging from 40 ± 11 mM for 2,2-bis(hydroxymethyl)malonate down to 57 ± 1 μM for 2,2-dichloromalonate, the most effective competitive mSR inhibitor known to date. The structure-activity relationship of the whole series in the human orthologue (hSR) was interpreted using Glide docking, WaterMap analysis of hydration and quantum mechanical calculations based on the X-ray structure of the hSR/malonate complex. Docking into the hSR active site with three thermodynamically favourable water molecules was able to discern qualitatively between good and weak inhibitors. Further improvement in ranking was obtained using advanced PM6-D3H4X/COSMO semiempirical quantum mechanics-based scoring which distinguished between the compounds with IC50 better/worse than 2 mM. We have thus not only found a new potent hSR inhibitor but also worked out a computer-assisted protocol to rationalize the binding affinity which will thus aid in search for more effective SR inhibitors. Novel, potent hSR inhibitors may represent interesting research tools as well as drug candidates for treatment of diseases associated with NMDA receptor overactivation. PMID:25462239

  3. Crystal structures of the wild-type, P1A mutant, and inactivated malonate semialdehyde decarboxylase: a structural basis for the decarboxylase and hydratase activities.

    PubMed

    Almrud, Jeffrey J; Poelarends, Gerrit J; Johnson, William H; Serrano, Hector; Hackert, Marvin L; Whitman, Christian P

    2005-11-15

    Malonate semialdehyde decarboxylase (MSAD) from Pseudomonas pavonaceae 170 is a tautomerase superfamily member that converts malonate semialdehyde to acetaldehyde by a mechanism utilizing Pro-1 and Arg-75. Pro-1 and Arg-75 have also been implicated in the hydratase activity of MSAD in which 2-oxo-3-pentynoate is processed to acetopyruvate. Crystal structures of MSAD (1.8 A resolution), the P1A mutant of MSAD (2.7 A resolution), and MSAD inactivated by 3-chloropropiolate (1.6 A resolution), a mechanism-based inhibitor activated by the hydratase activity of MSAD, have been determined. A comparison of the P1A-MSAD and MSAD structures reveals little geometric alteration, indicating that Pro-1 plays an important catalytic role but not a critical structural role. The structures of wild-type MSAD and MSAD covalently modified at Pro-1 by 3-oxopropanoate, the adduct resulting from the incubation of MSAD and 3-chloropropiolate, implicate Asp-37 as the residue that activates a water molecule for attack at C-3 of 3-chloropropiolate to initiate a Michael addition of water. The interactions of Arg-73 and Arg-75 with the C-1 carboxylate group of the adduct suggest these residues polarize the alpha,beta-unsaturated acid and facilitate the addition of water. On the basis of these structures, a mechanism for the inactivation of MSAD by 3-chloropropiolate can be formulated along with mechanisms for the decarboxylase and hydratase activities. The results also provide additional evidence supporting the hypothesis that MSAD and trans-3-chloroacrylic acid dehalogenase, a tautomerase superfamily member preceding MSAD in the trans-1,3-dichloropropene degradation pathway, diverged from a common ancestor but retained the key elements for the conjugate addition of water.

  4. Detection and quantification of glycosylated flavonoid malonates in celery, Chinese celery, and celery seed by LC-DAD-ESI/MS.

    PubMed

    Lin, Long-Ze; Lu, Shengmin; Harnly, James M

    2007-02-21

    A screening method using LC-DAD-ESI/MS was applied to the analysis of flavonoids in celery, Chinese celery, and celery seeds (Apium graveolens L. and varieties). Fifteen flavonoid glycosides were detected in the three celery materials. They were identified as luteolin 7-O-apiosylglucoside, luteolin 7-O-glucoside, apigenin 7-O-apiosylglucoside, chrysoeriol 7-O-apiosylglucoside, chrysoeriol 7-O-glucoside, and more than 10 malonyl derivatives of these glycosides. The identification of the malonyl derivatives was confirmed by their conversion into glycosides upon heating and by comparison of some of the malonates with malonates that had previously been identified in red bell pepper and parsley. The concentrations of the glycosides and the malonyl glycosides in the three materials were estimated by comparison to aglycone standards. This is the first report of the presence of these glycosylated flavonoid malonates in celery.

  5. Separation of no-carrier-added rhenium from bulk tantalum by the sodium malonate-PEG aqueous biphasic system.

    PubMed

    Dutta, Binita; Lahiri, Susanta; Tomar, B S

    2014-02-01

    The aqueous biphasic system (ABS) involving sodium malonate-polyethylene glycol (PEG) phases has been applied for the first time for separation of no-carrier-added (183)Re (T1/2=70 d) from α-particle irradiated bulk tantalum target. The various ABS conditions were applied for investigating the separation by varying pH, temperature, PEG-molecular weight, concentration of salt. The extraction pattern was hardly affected by change in pH and the molecular weight of PEG. One step separation of nca (183)Re from Ta was achieved at the optimal conditions of (i) 50% (w/w) PEG-4000-2 M sodium malonate, 40 °C and (ii) 50% (w/w) PEG-4000-3 M sodium malonate, room temperature (27 °C).

  6. 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…

  7. Histopathological occurrence and characterisation of calcium oxalate: a review.

    PubMed Central

    Chaplin, A J

    1977-01-01

    Oxalosis is the histological manifestation of a number of diverse clinicopathological states involving abnormalities of both endogenous and exogenous oxalate. Crystalline deposits of calcium oxalate, usually first detected by their birefringence, may be characterised by a combination of their physical and tinctorial properties. Images PMID:72077

  8. [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.

  9. 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. PMID:22492273

  10. 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.

  11. 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.

  12. Characterization of Medicago truncatula reduced calcium oxalate crystal mutant alleles

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  13. 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. PMID:26979820

  14. Reactive oxygen species and p38 mitogen-activated protein kinase activate Bax to induce mitochondrial cytochrome c release and apoptosis in response to malonate.

    PubMed

    Gomez-Lazaro, M; Galindo, M F; Melero-Fernandez de Mera, R M; Fernandez-Gómez, F J; Concannon, C G; Segura, M F; Comella, J X; Prehn, J H M; Jordan, J

    2007-03-01

    Malonate, an inhibitor of mitochondrial complex II, is a widely used toxin to study neurodegeneration in Huntington's disease and ischemic stroke. We have shown previously that malonate increased reactive oxygen species (ROS) production in human SH-SY5Y neuroblastoma cells, leading to oxidative stress, cytochrome c release, and apoptotic cell death. Expression of a green fluorescent protein-Bax fusion protein in SH-SY5Y neuroblastoma cells demonstrated a Bax redistribution from the cytosol to mitochondria after 12 to 24 h of malonate treatment that coincided with mitochondrial potential collapse and chromatin condensation. Inhibition of Bax translocation using furosemide, as well as Bax gene deletion, afforded significant protection against malonate-induced apoptosis. Further experiments revealed that malonate induced a prominent increase in the level of activated p38 mitogen-activated protein (MAP) kinase and that treatment with the p38 MAP kinase inhibitor SKF86002 potently blocked malonate-induced Bax translocation and apoptosis. Treatment with vitamin E diminished ROS production, reduced the activation status of p38 MAP kinase, inhibited Bax translocation, and protected against malonate-induced apoptosis. Our data suggest that malonate-induced ROS production and subsequent p38 MAP kinase activation mediates the activation of the pro-apoptotic Bax protein to induce mitochondrial membrane permeabilization and neuronal apoptosis.

  15. Crystal and molecular structure of a second, high-density polymorph of silver malonate

    NASA Astrophysics Data System (ADS)

    Prakasha Reddy, J.; Foxman, Bruce M.

    2008-11-01

    A new orthorhombic polymorph of silver malonate ( II) has been synthesized and structurally characterized. Compound II crystallizes in space group Pnma, with a = 12.8180(11), b = 9.2479(8), c = 4.0219(3) Å; V = 476.75(7) Å 3; Z = 4; ρcalc = 4.427 g cm -3. Full-matrix least-squares refinement converged to R1 = 0.0099 ( I > 2 σ( I), 765 data) and w R2 = 0.0264 ( F2, 785 data, 51 parameters). The familiar eight-membered Ag 2(RCO 2) 2 ring, characteristic of most silver(I) carboxylate complexes, has a Ag-Ag distance of 2.977(1) Å. Puckered sheets in the crystal ab plane are connected along c to form a three-dimensional coordination polymer. The density of II is >30% higher than that of the monoclinic polymorph ( I), first characterized in 1981. A survey of the density ratios of polymorphs in the Cambridge Structural Database indicates that virtually all of the pairs of entries having a density ratio >1.2 involve at least one form with significant void volume, as estimated using PLATON. However, neither I nor II have significant void volume, which suggests that the silver malonate polymorphs represent one of the largest density differences observed to date for a polymorphic pair. To date, it has not been possible to prepare I in our laboratories.

  16. Calcium Oxalate Crystals: An Integral Component of the Sclerotinia sclerotiorum/Brassica carinata Pathosystem

    PubMed Central

    Uloth, Margaret B.; Clode, Peta L.; You, Ming Pei; Barbetti, Martin J.

    2015-01-01

    Oxalic acid is an important virulence factor for disease caused by the fungal necrotrophic pathogen Sclerotinia sclerotiorum, yet calcium oxalate (CaOx) crystals have not been widely reported. B. carinata stems were infected with S. sclerotiorum and observed using light microscopy. Six hours post inoculation (hpi), CaOx crystals were evident on 46% of stem sections and by 72 hpi on 100%, demonstrating that the secretion of oxalic acid by S. sclerotiorum commences before hyphal penetration. This is the first time CaOx crystals have been reported on B. carinata infected with S. sclerotiorum. The shape of crystals varied as infection progressed. Long tetragonal rods were dominant 12 hpi (68% of crystal-containing samples), but by 72 hpi, 50% of stems displayed bipyramidal crystals, and only 23% had long rods. Scanning electron microscopy from 24 hpi revealed CaOx crystals in all samples, ranging from tiny irregular crystals (< 0.5 μm) to large (up to 40 μm) highly organized arrangements. Crystal morphology encompassed various forms, including tetragonal prisms, oval plates, crystal sand, and druses. Large conglomerates of CaOx crystals were observed in the hyphal mass 72 hpi and these are proposed as a strategy of the fungus to hold and detoxify Ca2+ions. The range of crystal morphologies suggests that S. sclerotiorum growth and infection controls the form taken by CaOx crystals. PMID:25816022

  17. Calcium oxalate crystals: an integral component of the Sclerotinia sclerotiorum/Brassica carinata pathosystem.

    PubMed

    Uloth, Margaret B; Clode, Peta L; You, Ming Pei; Barbetti, Martin J

    2015-01-01

    Oxalic acid is an important virulence factor for disease caused by the fungal necrotrophic pathogen Sclerotinia sclerotiorum, yet calcium oxalate (CaOx) crystals have not been widely reported. B. carinata stems were infected with S. sclerotiorum and observed using light microscopy. Six hours post inoculation (hpi), CaOx crystals were evident on 46% of stem sections and by 72 hpi on 100%, demonstrating that the secretion of oxalic acid by S. sclerotiorum commences before hyphal penetration. This is the first time CaOx crystals have been reported on B. carinata infected with S. sclerotiorum. The shape of crystals varied as infection progressed. Long tetragonal rods were dominant 12 hpi (68% of crystal-containing samples), but by 72 hpi, 50% of stems displayed bipyramidal crystals, and only 23% had long rods. Scanning electron microscopy from 24 hpi revealed CaOx crystals in all samples, ranging from tiny irregular crystals (< 0.5 μm) to large (up to 40 μm) highly organized arrangements. Crystal morphology encompassed various forms, including tetragonal prisms, oval plates, crystal sand, and druses. Large conglomerates of CaOx crystals were observed in the hyphal mass 72 hpi and these are proposed as a strategy of the fungus to hold and detoxify Ca2+ions. The range of crystal morphologies suggests that S. sclerotiorum growth and infection controls the form taken by CaOx crystals.

  18. Reevaluation of the plant "gemstones": Calcium oxalate crystals sustain photosynthesis under drought conditions.

    PubMed

    Tooulakou, Georgia; Giannopoulos, Andreas; Nikolopoulos, Dimosthenis; Bresta, Panagiota; Dotsika, Elissavet; Orkoula, Malvina G; Kontoyannis, Christos G; Fasseas, Costas; Liakopoulos, Georgios; Klapa, Maria I; Karabourniotis, George

    2016-09-01

    Land plants face the perpetual dilemma of using atmospheric carbon dioxide for photosynthesis and losing water vapors, or saving water and reducing photosynthesis and thus growth. The reason behind this dilemma is that this simultaneous exchange of gases is accomplished through the same minute pores on leaf surfaces, called stomata. In a recent study we provided evidence that pigweed, an aggressive weed, attenuates this problem exploiting large crystals of calcium oxalate as dynamic carbon pools. This plant is able to photosynthesize even under drought conditions, when stomata are closed and water losses are limited, using carbon dioxide from crystal decomposition instead from the atmosphere. Abscisic acid, an alarm signal that causes stomatal closure seems to be implicated in this function and for this reason we named this path "alarm photosynthesis." The so-far "enigmatic," but highly conserved and widespread among plant species calcium oxalate crystals seem to play a crucial role in the survival of plants.

  19. Two novel FeII-oxalate architectures: Solvent-free synthesis, structures, thermal and magnetic studies

    NASA Astrophysics Data System (ADS)

    Li, Jin-Hua; Liu, Hui; Wei, Li; Wang, Guo-Ming

    2015-10-01

    Two novel FeII-oxalate framework with the formulas of [NH4][FeIILi3(C2O4)3] (1) and [NH4]2[FeII(C2O4)2]·H2O (2) have been prepared by an oxalic acid flux approach and structurally characterized by IR, elemental analysis, thermogravimetric analysis, single-crystal and powder X-ray diffraction. Heterometallic compound 1 displays a three-dimensional (3D) framework with a pto topology, while homometallic compound 2 features a pillar-layer architecture with a hms topology. Thermal analysis indicates that the two compounds can be stable up to 300 °C and 200 °C, respectively. Magnetic investigations suggest that the FeII ions in 1 and 2 exhibit weak magnetic exchange interactions.

  20. Reevaluation of the plant "gemstones": Calcium oxalate crystals sustain photosynthesis under drought conditions.

    PubMed

    Tooulakou, Georgia; Giannopoulos, Andreas; Nikolopoulos, Dimosthenis; Bresta, Panagiota; Dotsika, Elissavet; Orkoula, Malvina G; Kontoyannis, Christos G; Fasseas, Costas; Liakopoulos, Georgios; Klapa, Maria I; Karabourniotis, George

    2016-09-01

    Land plants face the perpetual dilemma of using atmospheric carbon dioxide for photosynthesis and losing water vapors, or saving water and reducing photosynthesis and thus growth. The reason behind this dilemma is that this simultaneous exchange of gases is accomplished through the same minute pores on leaf surfaces, called stomata. In a recent study we provided evidence that pigweed, an aggressive weed, attenuates this problem exploiting large crystals of calcium oxalate as dynamic carbon pools. This plant is able to photosynthesize even under drought conditions, when stomata are closed and water losses are limited, using carbon dioxide from crystal decomposition instead from the atmosphere. Abscisic acid, an alarm signal that causes stomatal closure seems to be implicated in this function and for this reason we named this path "alarm photosynthesis." The so-far "enigmatic," but highly conserved and widespread among plant species calcium oxalate crystals seem to play a crucial role in the survival of plants. PMID:27471886

  1. The nucleation and growth of calcium oxalate monohydrate on self- assembled monolayers (SAMs)

    SciTech Connect

    Campbell, A.A.; Tarasevich, B.J.; Graff, G.L.; Fryxell, G.E.; Rieke, P.C.

    1992-05-01

    A physical chemical approach was used to study calcium oxalate monohydrate (COM) nucleation and growth on various organic interfaces. Self-assembling monolayers (SAMs), containing derivatized organic functional groups, were designed to mimic various amino acid residues present in both urine and stone matrix macromolecules. Derivatized surfaces include SAMs with terminal methyl, bromo, imidazole, and thiazolidine-carboxylic acid functional groups. Pronounced differences in COM deposition were observed for the various interfaces with the imidazole and thiazolidine surfaces having the greatest effect and the methyl and bromo groups having little or no nucleating potential.

  2. Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

    USGS Publications Warehouse

    Goldberg, M.C.; Cunningham, K.M.; Weiner, Eugene R.

    1993-01-01

    Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

  3. Wind tunnel investigations on the retention of carboxylic acids during riming

    NASA Astrophysics Data System (ADS)

    Jost, Alexander; Szakáll, Miklós; Diehl, Karoline; Mitra, Subir K.; Borrmann, Stephan

    2015-04-01

    In mid-latitudes, precipitation is mainly initiated via the ice phase in mixed phase clouds. In such clouds the ice particles grow to precipitation sizes at the expense of liquid drops through riming which means that supercooled droplets collide with ice particles and subsequently freeze. Water-soluble trace substances present in the liquid phase might remain only fractionally in the ice phase after freezing. This fractionation is called retention and is an important ratio which quantifies the partitioning of atmospheric trace substances between the phases. Laboratory experiments were carried out at the Mainz vertical wind tunnel to determine the retention of lower mono- and di-carboxylic acids during riming. Due to their low molecular weight and their polarity these acids are water-soluble. In the atmosphere formic acid and acetic acid are the most abundant mono-carboxylic acids in the gas and aqueous phase, thus, they represent the major fraction of carboxylic acids in cloud water. Oxalic and malonic acid are common coatings on aerosol particles because of their relatively low saturation vapor pressure. These di-carboxylic acids might therefore promote the aerosol particles to act as cloud condensation nuclei and additionally contribute to the aqueous phase chemistry in cloud droplets. The conditions during the riming experiments in the wind tunnel were similar to those in atmospheric mixed phase clouds, i.e. temperatures from -18°C to -6 °C, liquid water contents between 0.5 and 1.5 g/m3, and liquid drop radii between 10 and 20 μm. The liquid phase concentrations ranged from 3 to 5 mg/l (4.1 < pH < 4.5). As rime collectors captively floating ice particles and quasi-floating snowflakes with diameters between 0.6 and 1.5 cm were used. The wind speed in the vertical wind tunnel was very close to the terminal velocities of the rime collectors, thus, the ventilation during riming was in the same order of magnitude as under atmospheric riming conditions. After

  4. A calmodulin like EF hand protein positively regulates oxalate decarboxylase expression by interacting with E-box elements of the promoter

    PubMed Central

    Kamthan, Ayushi; Kamthan, Mohan; Kumar, Avinash; Sharma, Pratima; Ansari, Sekhu; Thakur, Sarjeet Singh; Chaudhuri, Abira; Datta, Asis

    2015-01-01

    Oxalate decarboxylase (OXDC) enzyme has immense biotechnological applications due to its ability to decompose anti-nutrient oxalic acid. Flammulina velutipes, an edible wood rotting fungus responds to oxalic acid by induction of OXDC to maintain steady levels of pH and oxalate anions outside the fungal hyphae. Here, we report that upon oxalic acid induction, a calmodulin (CaM) like protein-FvCaMLP, interacts with the OXDC promoter to regulate its expression. Electrophoretic mobility shift assay showed that FvCamlp specifically binds to two non-canonical E-box elements (AACGTG) in the OXDC promoter. Moreover, substitutions of amino acids in the EF hand motifs resulted in loss of DNA binding ability of FvCamlp. F. velutipes mycelia treated with synthetic siRNAs designed against FvCaMLP showed significant reduction in FvCaMLP as well as OXDC transcript pointing towards positive nature of the regulation. FvCaMLP is different from other known EF hand proteins. It shows sequence similarity to both CaMs and myosin regulatory light chain (Cdc4), but has properties typical of a calmodulin, like binding of 45Ca2+, heat stability and Ca2+ dependent electrophoretic shift. Hence, FvCaMLP can be considered a new addition to the category of unconventional Ca2+ binding transcriptional regulators. PMID:26455820

  5. Is Collective Intelligence (Mostly) the General Factor of Personality? A Comment on Woolley, Chabris, Pentland, Hashmi and Malone (2010)

    ERIC Educational Resources Information Center

    Woodley, Michael A.; Bell, Edward

    2011-01-01

    A recent paper [Woolley, Chabris, Pentland, Hashmi, & Malone. (2010). "Evidence for a collective intelligence factor in the performance of human groups." "Science", 330, 686-688] presents evidence for the existence of a general collective intelligence factor, "c," which may undergird performance on a variety of group tasks. This factor appears to…

  6. Effective DNA binding and cleaving tendencies of malonic acid coupled transition metal complexes

    NASA Astrophysics Data System (ADS)

    Pravin, Narayanaperumal; Utthra, Ponnukalai Ponya; Kumaravel, Ganesan; Raman, Natarajan

    2016-11-01

    Eight transition metal complexes were designed to achieve maximum biological efficacy. They were characterized by elemental analysis and various other spectroscopic techniques. The monomeric complexes were found to espouse octahedral geometry and non-electrolytic nature. The DNA interaction propensity of the complexes with calf thymus DNA (CT-DNA), studied at physiological pH by spectrophotometric, spectrofluorometric, cyclic voltammetry, and viscometric techniques revealed intercalation as the possible binding mode. Fascinatingly, the complexes were found to exhibit greater binding strength than that of the free ligands. A strong hypochromism and a slight red shift were exhibited by complex 5 among the other complexes. The intrinsic binding constant values of all the complexes compared to cisplatin reveal that they are excellent metallonucleases than that of cisplatin. The complexes were also shown to reveal displacement of the ethidium bromide, a strong intercalator using fluorescence titrations. Gel electrophoresis was used to divulge the competence of the complexes in cleaving the supercoiled pBR322 plasmid DNA. From the results, it is concluded that the complexes, especially 5, are excellent chemical nucleases in the presence of H2O2. Furthermore, the in vitro antimicrobial screening of the complexes exposes that these complexes are excellent antimicrobial agents. Overall the effect of coligands is evident from the results of all the investigations.

  7. Heterogeneous nucleation of calcium oxalate on native oxide surfaces

    SciTech Connect

    Song, L.; Pattillo, M.J.; Graff, G.L.; Campbell, A.A.; Bunker, B.C.

    1994-04-01

    The aqueous deposition of calcium oxalate onto colloidal oxides has been studied as a model system for understanding heterogeneous nucleation processes of importance in biomimetic synthesis of ceramic thin films. Calcium oxalate nucleation has been monitored by measuring induction times for nucleation using Constant Composition techniques and by measuring nucleation densities on extended oxide surfaces using an atomic force microscope. Results show that the dependence of calcium oxalate nucleation on solution supersaturation fits the functional form predicted by classical nucleation theories. Anionic surfaces appear to promote nucleation better than cationic surfaces, lowering the effective energy barrier to heterogeneous nucleation.

  8. Water-soluble dicarboxylic acids and ω-oxocarboxylic acids in size-segregated aerosols over northern Japan during spring: sources and formation processes

    NASA Astrophysics Data System (ADS)

    Deshmukh, Dhananjay Kumar; Kawamura, Kimitaka; Kobayashi, Minoru; Gowda, Divyavani

    2016-04-01

    Seven sets (AF01-AF07) of size-segregated aerosol (12-sizes) samples were collected using a Micro-Orifice Uniform Deposit Impactor (MOUDI) in Sapporo, Japan during the spring of 2001 to understand the sources and atmospheric processes of water-soluble organic aerosols in the outflow region of Asian dusts. The samples were analyzed for dicarboxylic acids (C2-C12) and ω-oxocarboxylic acids as well as inorganic ions. The molecular distribution of diacids showed the predominance of oxalic acid (C2) followed by malonic and succinic acids whereas ω-oxoacids showed the predominance of glyoxylic acid (ωC2) in size-segregated aerosols. SO42- and NH4+ are enriched in submicron mode whereas NO3- and Ca2+ are in supermicron mode. Most of diacids and ω-oxoacids are enriched in supermicron mode in the samples (AF01-AF03) influenced by the long-range transport of mineral dusts whereas enhanced presence in submicron mode was observed in other sample sets. The strong correlations of C2 with Ca2+ (r = 0.95-0.99) and NO3- (r = 0.96-0.98) in supermicron mode in the samples AF01-AF03 suggest the adsorption or production of C2 diacid via heterogeneous reaction on the surface of mineral dust during long-range atmospheric transport. The preferential enrichment of diacids and ω-oxoacids in mineral dust has important implications for the solubility and cloud nucleation properties of the dominant fraction of water-soluble organic aerosols. This study demonstrates that biofuel and biomass burning and mineral dust originated in East Asia are two major factors to control the size distribution of diacids and related compounds over northern Japan.

  9. Stable carbon isotopic compositions of total carbon, dicarboxylic acids and glyoxylic acid in the tropical Indian aerosols: Implications for sources and photochemical processing of organic aerosols

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.; Tachibana, Eri

    2011-09-01

    The tropical Indian aerosols (PM10) collected on day- and nighttime bases in winter and summer, 2007 from Chennai (13.04°N; 80.17°E) were studied for stable carbon isotopic compositions (δ13C) of total carbon (TC), individual dicarboxylic acids (C2-C9) and glyoxylic acid (ωC2). δ13C values of TC ranged from -23.9‰ to -25.9‰ (-25.0 ± 0.6‰; n = 49). Oxalic (C2) (-17.1 ± 2.5‰), malonic (C3) (-20.8 ± 1.8‰), succinic (C4) (-22.5 ± 1.5‰) and adipic (C6) (-20.6 ± 4.1‰) acids and ωC2 acid (-22.4 ± 5.5‰) were found to be more enriched with 13C compared to TC. In contrast, suberic (C8) (-29.4 ± 1.8‰), phthalic (Ph) (-30.1 ± 3.5‰) and azelaic (C9) (-28.4 ± 5.8‰) acids showed smaller δ13C values than TC. Based on comparisons of δ13C values of TC in Chennai aerosols to those (-24.7 ± 2.2‰) found in unburned cow-dung samples collected from Chennai and isotopic signatures of the particles emitted from point sources, we found that biofuel/biomass burning are the major sources of carbonaceous aerosols in South and Southeast Asia. The decrease in δ13C values of C9 diacid by about 5‰ from winter to summer suggests that tropical plant emissions also significantly contribute to organic aerosol in this region. Significant increase in δ13C values from C4 to C2 diacids in Chennai aerosols could be attributed for their photochemical processing in the tropical atmosphere during long-range transport from source regions.

  10. Determination of fluoride and oxalate using the indicator reaction of Zr(IV) with methylthymol blue adsorbed on silica gel.

    PubMed

    Zaporozhets, Olga A; Tsyukalo, Lyudmila Ye

    2007-07-30

    Solid-phase spectrophotometric and visual test-methods of fluoride and oxalate determination are proposed. The methods are based on the competitive reactions of ZrOCl2 with methylthymol blue immobilized on silica gel and fluoride or oxalate in solution. Absorbance of the solid-phase reagent at 590 nm decreases with the growth of fluoride and oxalate contents in solution. The developed methods demonstrate high selectivity. The interference of Bi(III) and SO4(2-), PO4(3-) is eliminated by the addition of 0.01 mol L(-1) solution of ascorbic acid and 0.01 mol L(-1) of BaCl2, respectively. To eliminate the fluoride interference with oxalate determination 1x10(-3) mol L(-1) solution of Ca(NO3)2 at pH 1.5 was added. The anions of the organic acids were destructed prior to F- determination by ultrasonic exposition (44 kHz, intensity of < or = 10 W cm(-2) for 3 min). The proposed methods were applied to the analysis of mineral water, toothpaste and biological fluids.

  11. High-sensitivity microchip electrophoresis determination of inorganic anions and oxalate in atmospheric aerosols with adjustable selectivity and conductivity detection.

    PubMed

    Noblitt, Scott D; Schwandner, Florian M; Hering, Susanne V; Collett, Jeffrey L; Henry, Charles S

    2009-02-27

    A sensitive and selective separation of common anionic constituents of atmospheric aerosols, sulfate, nitrate, chloride, and oxalate, is presented using microchip electrophoresis. The optimized separation is achieved in under 1 min and at low background electrolyte ionic strength (2.9 mM) by combining a metal-binding electrolyte anion (17 mM picolinic acid), a sulfate-binding electrolyte cation (19 mM HEPBS), a zwitterionic surfactant with affinity towards weakly solvated anions (19 mM N-tetradecyl,N,N-dimethyl-3-ammonio-1-propansulfonate), and operation in counter-electroosmotic flow (EOF) mode. The separation is performed at pH 4.7, permitting pH manipulation of oxalate's mobility. The majority of low-concentration organic acids are not observed at these conditions, allowing for rapid subsequent injections without the presence of interfering peaks. Because the mobilities of sulfate, nitrate, and oxalate are independently controlled, other minor constituents of aerosols can be analyzed, including nitrite, fluoride, and formate if desired using similar separation conditions. Contact conductivity detection is utilized, and the limit of detection for oxalate (S/N=3) is 180 nM without stacking. Sensitivity can be increased with field-amplified sample stacking by injecting from dilute electrolyte with a detection limit of 19 nM achieved. The high-sensitivity, counter-EOF operation, and short analysis time make this separation well-suited to continuous online monitoring of aerosol composition.

  12. Nitrate reduction by zerovalent iron: effects of formate, oxalate, citrate, chloride, sulfate, borate, and phosphate.

    PubMed

    Su, Chunming; Puls, Robert W

    2004-05-01

    Recent studies have shown that zerovalent iron (Fe0) may potentially be used as a chemical medium in permeable reactive barriers (PRBs) for groundwater nitrate remediation; however, the effects of commonly found organic and inorganic ligands in soil and sediments on nitrate reduction by Fe0 have not been well understood. A 25.0 mL nitrate solution of 20.0 mg of N L(-1) (1.43 mM nitrate) was reacted with 1.00 g of Peerless Fe0 at 200 rpm on a rotational shaker at 23 degrees C for up to 120 h in the presence of each of the organic acids (3.0 mM formic, 1.5 mM oxalic, and 1.0 mM citric acids) and inorganic acids (3.0 mM HCl, 1.5 mM H2SO4, 3.0 mM H3BO3, and 1.5 mM H3PO4). These acids provided an initial dissociable H+ concentration of 3.0 mM available for nitrate reduction reactions under conditions of final pH < 9.3. Nitrate reduction rates (pseudo-first-order) increased in the order: H3PO4 < citric acid < H3BO3 < oxalic acid < H2SO4 < formic acid < HCl, ranging from 0.00278 to 0.0913 h(-1), corresponding to surface area normalized rates ranging from 0.126 to 4.15 h(-1) m(-2) mL. Correlation analysis showed a negative linear relationship between the nitrate reduction rates for the ligands and the conditional stability constants for the soluble complexes of the ligands with Fe2+ (R2 = 0.701) or Fe3+ (R2 = 0.918) ions. This sequence of reactivity corresponds also to surface adsorption and complexation of the three organic ligands to iron oxides, which increase in the order formate < oxalate < citrate. The results are also consistent with the sequence of strength of surface complexation of the inorganic ligands to iron oxides, which increases in the order: chloride < sulfate < borate < phosphate. The blockage of reactive sites on the surface of Fe0 and its corrosion products by specific adsorption of the inner-sphere complex forming ligands (oxalate, citrate, sulfate, borate, and phosphate) may be responsible for the decreased nitrate reduction by Fe0 relative to the

  13. A study of thermal, dielectric and magnetic properties of strontium malonate crystals

    NASA Astrophysics Data System (ADS)

    Mathew, Varghese; Jacob, Sabu; Mahadevan, C. K.; Abraham, K. E.

    2012-01-01

    Crystals of strontium malonate (SrC 3H 2O 4) were grown in silica gel by the single diffusion technique. The thermo gravimetric (TG), differential thermal analysis (DTA) and differential scanning calorimetric (DSC) studies were carried out to investigate the thermal stability of the crystal. The dielectric behavior of the title compound crystal was investigated by measuring the dielectric parameters - dielectric constant, dielectric loss and AC conductivity as a function of four frequencies -1 kHz, 10 kHz, 100 kHz and 1 MHz at temperatures ranging from 50 to 170 °C. Results indicate that the title compound is thermally stable up to about 409 °C and is a promising low εr-value dielectric material. The magnetic behavior of the crystal was also explored using a vibrating sample magnetometer.

  14. The Structure of an Oxalate Oxidoreductase Provides Insight into Microbial 2-Oxoacid Metabolism

    PubMed Central

    2016-01-01

    Thiamine pyrophosphate (TPP), a derivative of vitamin B1, is a versatile and ubiquitous cofactor. When coupled with [4Fe-4S] clusters in microbial 2-oxoacid:ferredoxin oxidoreductases (OFORs), TPP is involved in catalyzing low-potential redox reactions that are important for the synthesis of key metabolites and the reduction of N2, H+, and CO2. We have determined the high-resolution (2.27 Å) crystal structure of the TPP-dependent oxalate oxidoreductase (OOR), an enzyme that allows microbes to grow on oxalate, a widely occurring dicarboxylic acid that is found in soil and freshwater and is responsible for kidney stone disease in humans. OOR catalyzes the anaerobic oxidation of oxalate, harvesting the low-potential electrons for use in anaerobic reduction and fixation of CO2. We compare the OOR structure to that of the only other structurally characterized OFOR family member, pyruvate:ferredoxin oxidoreductase. This side-by-side structural analysis highlights the key similarities and differences that are relevant for the chemistry of this entire class of TPP-utilizing enzymes. PMID:26061898

  15. Rapid oxalate determination in blood and synthetic urine using a newly developed oxometer.

    PubMed

    Canales, Benjamin K; Richards, Nigel G; Peck, Ammon B

    2013-02-01

    Blood and urine oxalate determinations have been limited to the laboratory setting because of complex sample storage and processing methods as well as the need for color spectrophotometry and ion chromatography. We hypothesized that glucometer test strips, impregnated with glucose oxidase and dyes that measure secondary hydrogen peroxide production, could be infused with oxalate oxidase and produce enhanced color changes in the presence of oxalate. By increasing the amount of sodium oxalate in fresh blood, we found that glucometer-measured oxalate increased on a linear scale. In addition, oxalate levels in synthetic urine could be measured using a visual scale, suggesting that strip dwell time or oxalate/oxalate oxidase concentrations could be manipulated to enhance optimal sensitivity. Although further testing is necessary, this simple, first-generation oxometer may eventually allow point of care testing in the home or office, empowering patients with oxalate-based medical conditions and giving healthcare providers real-time oxalate feedback.

  16. Crystallization kinetics of calcium oxalate hydrates studied by scanning confocal interference microscopy

    NASA Astrophysics Data System (ADS)

    Grohe, Bernd; Rogers, Kem A.; Goldberg, Harvey A.; Hunter, Graeme K.

    2006-10-01

    Scanning confocal interference microscopy (SCIM) is an optical technique that allows the visualization of structures below the limits of classical optical microscopy (≪250 nm). This study represents the first use of SCIM to analyze the formation of calcium oxalate crystals, the major constituent of kidney stones. Crystals were nucleated and grown on the glass bottom of Petri dishes in the presence and absence of the polyelectrolyte inhibitor poly- L-aspartic acid (poly-asp). In the absence of poly-asp, monoclinic calcium oxalate monohydrate (COM) nucleated from {1 0 0} or {0 1 0} faces. The first observed particles were 70-120 nm in diameter and grew by a step-like progression in the [0 0 1] and [0 1 0] directions. Addition of poly-asp had several effects on calcium oxalate formation. First, the number of particles was increased, but their sizes were decreased. Second, the rate of COM growth in the [0 0 1] direction was decreased to a greater extent than the rate along [0 1 0]. Third, the formation of tetragonal calcium oxalate dihydrate (COD) crystals was favored. Fourth, the rates of COD growth along <1 1 0> and allied directions were decreased, whereas that parallel to <0 0 1> is increased. Sequences of highly resolved growth fronts show step displacement for COM and moving crystal edges for COD. Analysis of image sequences suggested that growth is strongly affected by competing and alternating processes, in which diffusion processes are rate-limiting and induce nonlinear growth. This study shows that SCIM is a powerful technique for the quantitative analysis of crystallization processes and for determining the mode of action of inhibitors.

  17. Risk factors associated with calcium oxalate urolithiasis in dogs evaluated at general care veterinary hospitals in the United States.

    PubMed

    Okafor, Chika C; Lefebvre, Sandra L; Pearl, David L; Yang, Mingyin; Wang, Mansen; Blois, Shauna L; Lund, Elizabeth M; Dewey, Cate E

    2014-08-01

    Calcium oxalate urolithiasis results from the formation of aggregates of calcium salts in the urinary tract. Difficulties associated with effectively treating calcium oxalate urolithiasis and the proportional increase in the prevalence of calcium oxalate uroliths relative to other urolith types over the last 2 decades has increased the concern of clinicians about this disease. To determine factors associated with the development of calcium oxalate urolithiasis in dogs evaluated at general care veterinary hospitals in the United States, a retrospective case-control study was performed. A national electronic database of medical records of all dogs evaluated between October 1, 2007 and December 31, 2010 at 787 general care veterinary hospitals in the United States was reviewed. Dogs were selected as cases at the first-time diagnosis of a laboratory-confirmed urolith comprised of at least 70% calcium oxalate (n=452). Two sets of control dogs with no history of urolithiasis diagnosis were randomly selected after the medical records of all remaining dogs were reviewed: urinalysis examination was a requirement in the selection of one set (n=1808) but was not required in the other set (n=1808). Historical information extracted included urolith composition, dog's diet, age, sex, neuter status, breed size category, hospital location, date of diagnosis, and urinalysis results. Multivariable analysis showed that the odds of first-time diagnosis of calcium oxalate urolithiasis were significantly (P<0.05) greater for dogs<7 years, males (OR: 7.77, 95% CI: 4.93-12.26), neutered (OR: 2.58, 1.44-4.63), toy- vs. medium-sized breeds (OR: 3.15, 1.90-5.22), small- vs. medium-sized breeds (OR: 3.05, 1.83-5.08), large- vs. medium-sized breeds (OR: 0.05, 0.01-0.19), and those with a diagnosis of cystitis within the previous year (OR: 6.49, 4.14-10.16). Urinary factors significantly associated with first-time diagnosis of calcium oxalate urolithiasis were acidic vs. basic pH (OR: 1.94, 1

  18. Multiorgan crystal deposition following intravenous oxalate infusion in rat

    SciTech Connect

    Blumenfrucht, M.J.; Cheeks, C.; Wedeen, R.P.

    1986-06-01

    Deposition of calcium oxalate is responsible for the pathologic manifestations of oxalosis and may contribute to multiorgan dysfunction in uremia and to the progression of renal damage after renal failure is established. We have developed a rat model of oxalosis using a single intravenous injection of sodium oxalate, 0.3 mmol./kg. body weight, in rats. Polarized light microscopy and section freeze-dry autoradiography were used to identify /sup 14/C-oxalate within the renal parenchyma and in extrarenal organs. /sup 14/C-oxalate crystals under three mu in length were identified within one min. of injection in proximal tubule lumens. Section freeze-dry autoradiography showed occasional minute crystals within glomeruli, heart, lung and liver at one hr. In contrast to concentrative cellular uptake demonstrated in rat renal cortical slices in vitro, intracellular accumulation of /sup 14/C-oxalate could not be detected in vivo. Within the first 24 hr., renal oxalate retention reached a maximum of 25 +/- 4 per cent of the injected dose/gm. kidney compared to a maximum of only 7 +/- 3 per cent/gm. kidney after intraperitoneal administration. Although less than one per cent dose/gm. kidney remained after one week, crystal fragments were scattered throughout the cortex and medulla, often surrounded by foci of interstitial nephritis. The retention of crystals in kidney and other body organs following i.v. oxalate provides a model of oxalosis which stimulates pathophysiologic events in a variety of clinical situations characterized by transiently or persistently elevated serum oxalate.

  19. 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

  20. Oxalate nephropathy in free-living American bullfrog tadpoles.

    PubMed

    Tokiwa, Toshihiro; Kadekaru, Sho; Ito, Masao; Yoshida, Makoto; Une, Yumi

    2015-10-27

    In February 2014, wild American bullfrog Lithobates catesbeianus tadpoles from an artificial pond in the Kyusyu region, Japan, presented with coelomic and subcutaneous edema and erythema within the skin. A pathological examination of 57 tadpoles of American bullfrogs in the region was conducted to evaluate the disease. Crystal deposition of varying degrees was found in the kidneys of 35 tadpoles (61.4%). The crystals were transparent, pleomorphic in shape, highly birefringent in polarized light, and arranged in a radial pattern within the renal tubular lumen. Using Alizarin Red S stain and liquid chromatography, these crystals were identified as calcium oxalate. Severe coelomic and subcutaneous edema was observed in 7 of these 35 tadpoles (20.0%). Ammonia levels in coelomic fluid were extremely elevated (>1000 µg dl(-1)) in 4 tadpoles examined. These findings suggest that oxalate deposition in kidneys causes metabolic disorder with renal nephropathy. The source of the oxalate could not be determined; however, the presence of calcium oxalates in pond sediments, as revealed by liquid chromatography, suggested that the deposition was most likely due to ingestion of oxalate materials from the environment. This is the first report of oxalate nephropathy in free-living amphibians. PMID:26503774

  1. 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.

  2. Oxalate nephropathy in free-living American bullfrog tadpoles.

    PubMed

    Tokiwa, Toshihiro; Kadekaru, Sho; Ito, Masao; Yoshida, Makoto; Une, Yumi

    2015-10-27

    In February 2014, wild American bullfrog Lithobates catesbeianus tadpoles from an artificial pond in the Kyusyu region, Japan, presented with coelomic and subcutaneous edema and erythema within the skin. A pathological examination of 57 tadpoles of American bullfrogs in the region was conducted to evaluate the disease. Crystal deposition of varying degrees was found in the kidneys of 35 tadpoles (61.4%). The crystals were transparent, pleomorphic in shape, highly birefringent in polarized light, and arranged in a radial pattern within the renal tubular lumen. Using Alizarin Red S stain and liquid chromatography, these crystals were identified as calcium oxalate. Severe coelomic and subcutaneous edema was observed in 7 of these 35 tadpoles (20.0%). Ammonia levels in coelomic fluid were extremely elevated (>1000 µg dl(-1)) in 4 tadpoles examined. These findings suggest that oxalate deposition in kidneys causes metabolic disorder with renal nephropathy. The source of the oxalate could not be determined; however, the presence of calcium oxalates in pond sediments, as revealed by liquid chromatography, suggested that the deposition was most likely due to ingestion of oxalate materials from the environment. This is the first report of oxalate nephropathy in free-living amphibians.

  3. Extraction and estimation of the quantity of calcium oxalate crystals in the foliage of conifer and hardwood trees.

    PubMed

    Minocha, Rakesh; Chamberlain, Bradley; Long, Stephanie; Turlapati, Swathi A; Quigley, Gloria

    2015-05-01

    The main goal of this study was to develop a method for the extraction and indirect estimation of the quantity of calcium oxalate (CaOx) in the foliage of trees. Foliar tissue was collected from a single tree of each species (five conifers and five hardwoods) for comparison of extractions in different solvents using 10 replicates per species from the same pool of tissue. For each species, calcium (Ca) and oxalate were extracted sequentially in double deionized water and 2N acetic acid, and finally, five replicate samples were extracted in 5% (0.83N) perchloric acid (PCA) and the other five in 2N hydrochloric acid (HCl); three cycles of freezing and thawing were used for each solvent. Total ions were extracted by microwave digestion. Calcium was quantified with an inductively coupled plasma emission spectrophotometer method and oxalate was eluted and quantified using a high performance liquid chromatography method. This experiment was repeated again with two conifer and two hardwood species using four trees per species, and two analytical replicates for each tree. We report here that, regardless of age of individual trees within a species, time of collection or species type, the third extraction in PCA or HCl resulted in near equimolar quantities of Ca and oxalate (r(2) ≥ 0.99). This method provides an easy estimate of the quantity of CaOx crystals using a small sample of foliar tissue. An additional benefit of PCA is that it precipitates the nucleic acids and proteins, allowing the quantification of several free/soluble metabolites such as amino acids, polyamines, organic acids and inorganic elements all from a single sample extract. PMID:25934989

  4. Extraction and estimation of the quantity of calcium oxalate crystals in the foliage of conifer and hardwood trees.

    PubMed

    Minocha, Rakesh; Chamberlain, Bradley; Long, Stephanie; Turlapati, Swathi A; Quigley, Gloria

    2015-05-01

    The main goal of this study was to develop a method for the extraction and indirect estimation of the quantity of calcium oxalate (CaOx) in the foliage of trees. Foliar tissue was collected from a single tree of each species (five conifers and five hardwoods) for comparison of extractions in different solvents using 10 replicates per species from the same pool of tissue. For each species, calcium (Ca) and oxalate were extracted sequentially in double deionized water and 2N acetic acid, and finally, five replicate samples were extracted in 5% (0.83N) perchloric acid (PCA) and the other five in 2N hydrochloric acid (HCl); three cycles of freezing and thawing were used for each solvent. Total ions were extracted by microwave digestion. Calcium was quantified with an inductively coupled plasma emission spectrophotometer method and oxalate was eluted and quantified using a high performance liquid chromatography method. This experiment was repeated again with two conifer and two hardwood species using four trees per species, and two analytical replicates for each tree. We report here that, regardless of age of individual trees within a species, time of collection or species type, the third extraction in PCA or HCl resulted in near equimolar quantities of Ca and oxalate (r(2) ≥ 0.99). This method provides an easy estimate of the quantity of CaOx crystals using a small sample of foliar tissue. An additional benefit of PCA is that it precipitates the nucleic acids and proteins, allowing the quantification of several free/soluble metabolites such as amino acids, polyamines, organic acids and inorganic elements all from a single sample extract.

  5. Boric Acid Adsorption onto Humic Acids: Structures, Stabilities, 11B NMR and 11B,10B Isotopic Fractionations of Surface Complexes

    NASA Astrophysics Data System (ADS)

    Tossell, J. A.

    2006-05-01

    Boric acid, B(OH)3, forms complexes in aqueous solution with a number of bidentate O-containing ligands, L- 2, such as C2O4-2 (oxalate), C3H2O4-2 (malonate), C2H4O2-2 (glycolate), C6H4O2-2 (catecholate) and C10H6O2-2 (dioxynaphthalene). McElligot and Byrne (1998) have also found it to form a complex with CO3-2. Recently Lemarchand, et al. (2005) have studied the formation of surface complexes of B(OH)3 on humic acid, determining formation constants, 11B NMR shifts and 11B,10B isotope fractionations for a number of such complexes. This helps to clarify both the interaction of boric acid with the humic acid and the nature of the coordinating sites on the humic acid. The determination of isotope fractionations may be seen as a form of vibrational spectroscopy, using the fractionating element as a local probe of the vibrational spectrum which determines the fractionation. We have calculated quantum mechanically the structures, stabilities, vibrational spectra, 11B NMR spectra and 11B,110B isotope fractionations of a number of complexes B(OH)2L- formed by reactions of the type: B(OH)3 + HL- ? B(OH)2L- + H2O (1) using the 6-311G(d,p) B3LYP method for structures and isotopic fractionations, the highly accurate Complete Basis Set-QB3 method for energetics and the GIAO HF method with a 6-311+G(2d,p) basis for the NMR shieldings. Oxalic acid, malonic acid and catechol all form stable complexes (?G<0 for reaction 1),which are deshielded (less negative ?) vs. B(OH)4- by 2.7, 0.6 and 5.6 ppm, respectively, and which are isotopically lighter than B(OH)4- (more negative ? 11B) by 3, 2 and 5 ‰, respectively. The calculated 11B NMR shifts match well with the results of Lemarchand, et al. (2005) while the calculated isotopic fractionations are qualitatively consistent with their results, but show much smaller deviations from B(OH)4-. This is probably a consequence of the use by these authors of a value of 1.0194 (Kakihana, et al., 1977) for the 11B,10B isotopic exchange

  6. Utilizing maleic acid as a novel fuel for synthesis of PbFe{sub 12}O{sub 19} nanoceramics via sol–gel auto-combustion route

    SciTech Connect

    Ansari, Fatemeh; Soofivand, Faezeh; Salavati-Niasari, Masoud

    2015-05-15

    PbFe{sub 12}O{sub 19} nanostructures were prepared in an aqueous solution by the sol–gel auto-combustion method using Pb(NO{sub 3}){sub 2} and Fe(NO{sub 3}){sub 3} as starting materials and various carboxylic acids, including oxalic acid, malonic acid, succinic acid and maleic acid as fuel and reducing and capping agents. The as-synthesized products were characterized by X- ray diffraction, scanning electron microscopy, and X-ray energy dispersive spectroscopy. The effect of carboxylic acid type, Pb{sup +} {sup 2} to carboxylic acid molar ratio, and calcination temperature was investigated on the morphology of the products and several experiments were carried out to obtain the optimal reaction conditions. It was found that the phase and the morphology of the products are influenced by the investigated parameters. Furthermore, vibrating sample magnetometer (VSM) was used to study the magnetic properties of PbFe{sub 12}O{sub 19} samples. - Graphical abstract: Display Omitted - Highlights: • PbFe{sub 12}O{sub 19} nanoceramics were synthesized from Fe(NO{sub 3}){sub 3} and Pb(NO{sub 3}){sub 2} via the sol–gel auto combustion method. • The maleic acid can be instead of common capping agent and fuel in auto-combustion sol–gel. • The synthesized PbFe{sub 12}O{sub 19} is a hard magnetic material. • The specific saturation magnetization and coercivity are 27 emu/g and 1900 Oe, respectively.

  7. Organic Acids: The Pools of Fixed Carbon Involved in Redox Regulation and Energy Balance in Higher Plants

    PubMed Central

    Igamberdiev, Abir U.; Eprintsev, Alexander T.

    2016-01-01

    Organic acids are synthesized in plants as a result of the incomplete oxidation of photosynthetic products and represent the stored pools of fixed carbon accumulated due to different transient times of conversion of carbon compounds in metabolic pathways. When redox level in the cell increases, e.g., in conditions of active photosynthesis, the tricarboxylic acid (TCA) cycle in mitochondria is transformed to a partial cycle supplying citrate for the synthesis of 2-oxoglutarate and glutamate (citrate valve), while malate is accumulated and participates in the redox balance in different cell compartments (via malate valve). This results in malate and citrate frequently being the most accumulated acids in plants. However, the intensity of reactions linked to the conversion of these compounds can cause preferential accumulation of other organic acids, e.g., fumarate or isocitrate, in higher concentrations than malate and citrate. The secondary reactions, associated with the central metabolic pathways, in particularly with the TCA cycle, result in accumulation of other organic acids that are derived from the intermediates of the cycle. They form the additional pools of fixed carbon and stabilize the TCA cycle. Trans-aconitate is formed from citrate or cis-aconitate, accumulation of hydroxycitrate can be linked to metabolism of 2-oxoglutarate, while 4-hydroxy-2-oxoglutarate can be formed from pyruvate and glyoxylate. Glyoxylate, a product of either glycolate oxidase or isocitrate lyase, can be converted to oxalate. Malonate is accumulated at high concentrations in legume plants. Organic acids play a role in plants in providing redox equilibrium, supporting ionic gradients on membranes, and acidification of the extracellular medium. PMID:27471516

  8. Organic Acids: The Pools of Fixed Carbon Involved in Redox Regulation and Energy Balance in Higher Plants.

    PubMed

    Igamberdiev, Abir U; Eprintsev, Alexander T

    2016-01-01

    Organic acids are synthesized in plants as a result of the incomplete oxidation of photosynthetic products and represent the stored pools of fixed carbon accumulated due to different transient times of conversion of carbon compounds in metabolic pathways. When redox level in the cell increases, e.g., in conditions of active photosynthesis, the tricarboxylic acid (TCA) cycle in mitochondria is transformed to a partial cycle supplying citrate for the synthesis of 2-oxoglutarate and glutamate (citrate valve), while malate is accumulated and participates in the redox balance in different cell compartments (via malate valve). This results in malate and citrate frequently being the most accumulated acids in plants. However, the intensity of reactions linked to the conversion of these compounds can cause preferential accumulation of other organic acids, e.g., fumarate or isocitrate, in higher concentrations than malate and citrate. The secondary reactions, associated with the central metabolic pathways, in particularly with the TCA cycle, result in accumulation of other organic acids that are derived from the intermediates of the cycle. They form the additional pools of fixed carbon and stabilize the TCA cycle. Trans-aconitate is formed from citrate or cis-aconitate, accumulation of hydroxycitrate can be linked to metabolism of 2-oxoglutarate, while 4-hydroxy-2-oxoglutarate can be formed from pyruvate and glyoxylate. Glyoxylate, a product of either glycolate oxidase or isocitrate lyase, can be converted to oxalate. Malonate is accumulated at high concentrations in legume plants. Organic acids play a role in plants in providing redox equilibrium, supporting ionic gradients on membranes, and acidification of the extracellular medium. PMID:27471516

  9. Preclinical Evaluation of Antiurolithiatic Activity of Viburnum opulus L. on Sodium Oxalate-Induced Urolithiasis Rat Model

    PubMed Central

    İlhan, Mert; Ergene, Burçin; Süntar, Ipek; Özbilgin, Serkan; Saltan Çitoğlu, Gülçin; Demirel, M. Ayşe; Keleş, Hikmet; Altun, Levent; Küpeli Akkol, Esra

    2014-01-01

    The aim of the present research is to evaluate the antiurolithiatic effect of the various extracts prepared from the fruits of Viburnum opulus L., in regard to its ethnobotanical record. To induce urolithiasis, 70 mg/kg sodium oxalate was injected to the rats which were housed individually in metabolic cages. The test materials were applied during 7 days. Biochemical (urine and serum parameters), histopathological and antioxidant (TBARs, TSH and GSH) assays were conducted. The urine samples were examined by light microscope for the determination of the calcium oxalate crystals. Lyophilized juice of V. opulus (LJVO) and lyophilized commercial juice of V. opulus (LCJVO) exerted potential antiurolithiatic activity which was attributed to its diuretic effect along with the inhibitory action on the oxalate levels and free radical production. We also determined the chlorogenic acid content of the LJVO by high-performance liquid chromatography (HPLC). Chlorogenic acid was determined by using Supelcosil LC-18 (250 × 4.6 mm, 5 µm) column and acetonitrile: water: 0.2% o-phosphoric acid as a mobile phase. The chlorogenic acid content of V. opulus was found to be 0.3227 mg/mL in fruit juice. The results obtained in this study have provided a scientific evidence for the traditional usage of V. opulus on passing kidney stones in Turkish folk medicine. PMID:25165481

  10. Crystal structure of 2-methyl-1H-imidazol-3-ium hydrogen oxalate dihydrate.

    PubMed

    Diop, Mouhamadou Birame; Diop, Libasse; Plasseraud, Laurent; Cattey, Hélène

    2016-08-01

    Single crystals of the title mol-ecular salt, C4H7N2 (+)·HC2O4 (-)·2H2O, were isolated from the reaction of 2-methyl-1H-imidazole and oxalic acid in a 1:1 molar ratio in water. In the crystal, the cations and anions are positioned alternately along an infinite [010] ribbon and linked together through bifurcated N-H⋯(O,O) hydrogen bonds. The water mol-ecules of crystallization link the chains into (10-1) bilayers, with the methyl groups of the cations organized in an isotactic manner. PMID:27536393

  11. Crystal structure of 2-methyl-1H-imidazol-3-ium hydrogen oxalate dihydrate

    PubMed Central

    Diop, Mouhamadou Birame; Diop, Libasse; Plasseraud, Laurent; Cattey, Hélène

    2016-01-01

    Single crystals of the title mol­ecular salt, C4H7N2 +·HC2O4 −·2H2O, were isolated from the reaction of 2-methyl-1H-imidazole and oxalic acid in a 1:1 molar ratio in water. In the crystal, the cations and anions are positioned alternately along an infinite [010] ribbon and linked together through bifurcated N—H⋯(O,O) hydrogen bonds. The water mol­ecules of crystallization link the chains into (10-1) bilayers, with the methyl groups of the cations organized in an isotactic manner. PMID:27536393

  12. In vitro ruminal fermentation of organic acids common in forage.

    PubMed Central

    Russell, J B; Van Soest, P J

    1984-01-01

    Mixed rumen bacteria from cows fed either timothy hay or a 60% concentrate were incubated with 7.5 mM citrate, trans-aconitate, malate, malonate, quinate, and shikimate. Citrate, trans-aconitate, and malate were fermented at faster rates than malonate, quinate, and shikimate. Acetate was the primary fermentation product for all six acids. Quinate and shikimate fermentations gave rist to butyrate, whereas malate and malonate produced significant amounts of propionic acid. High-pressure liquid chromatography of fermentation products from trans-aconitate incubations revealed a compound that was subsequently identified as tricarballylate. As much as 40% of the trans-aconitate acid was converted to tricarballylate, and tricarballylate was fermented slowly. The slow rate of tricarballylate metabolism by mixed rumen bacteria and its potential as a magnesium chelator suggest that tricarballylate formation could be an important factor in the hypomagnesemia that leads to grass tetany. PMID:6696413

  13. Local structure and molecular motions in imidazolium hydrogen malonate crystal as studied by 2H and 13C NMR

    NASA Astrophysics Data System (ADS)

    Mizuno, M.; Chizuwa, M.; Umiyama, T.; Kumagai, Y.; Miyatou, T.; Ohashi, R.; Ida, T.; Tansho, M.; Shimizu, T.

    2015-04-01

    The local structure and molecular motion of the imidazolium hydrogen malonate crystal were investigated using solid-state 2H and 13C NMR. The imidazolium ion undergoes isotropic rotation, which is correlated with a defect in the crystal, as observed by 2H NMR broadline spectra above 263 K. A 180∘ flip of the imidazolium ion in the regular site was observed from 2H NMR quadrupole Carr-Purcell-Meiboom-Gill (QCPMG) spectra. The Grotthuss mechanism was accompanied by a 180∘ flip of the imidazolium ion in regular sites. Moreover, the proton transfer associated with the imidazolium ion of the defective crystal is important for proton conductivity of the imidazolium hydrogen malonate crystal.

  14. 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

  15. [Determination of glyoxalate and oxalate by capillary zone electrophoresis].

    PubMed

    Guan, Jin; Wang, Huize; Ren, Liyan; Niu, Qiuling

    2012-01-01

    A method for the simultaneous determination of glyoxalate and oxalate by capillary zone electrophoresis (CZE) was developed. The influences of type, concentration and pH of the running buffer, and the applied voltage on separation were investigated. Glyoxalate and oxalate were separated within 11 min under the conditions of 20 mmol/L borax-5.5 mmol/L potassium hydrogen phthalate (pH 9.0), applied voltage of 20 kV, and detected wavelength of 212 nm. The calibration curves of glyoxalate and oxalate showed good linearity in the ranges of 0.8 -20 g/L and 1.2-20 g/L, respectively. The correlation coefficients were 0.999 3 and 0.997 5, respectively. The limits of detection for glyoxalate and oxalate were 0.2 and 0.4 g/L (S/N = 3), respectively. The average recoveries at three spiked levels were 98.3%-102.5% with acceptable relative standard deviations of 0.35%-0.61%. This method is simple, low cost and high performance. The method was successfully used for the determination of glyoxalate and oxalate in real samples, and the assay results were satisfactory. PMID:22667103

  16. Column liquid chromatography-ultraviolet and column liquid chromatography/mass spectrometry evaluation of stress degradation behavior of escitalopram oxalate.

    PubMed

    Dhaneshwar, Sunil R; Mahadik, Mahadeo V; Kulkarni, Mahesh J

    2009-01-01

    The objective of this work was to study the degradation behavior of escitalopram oxalate under different International Conference on Harmonization (ICH)-recommended stress conditions by column liquid chromatography (LC)-UV and LC/mass spectrometry (LC/MS) and to establish a validated stability-indicating LC assay method. Escitalopram oxalate was subjected to stress conditions of hydrolysis, oxidation, photolysis, and thermal decomposition. Extensive degradation was found to occur in alkaline medium. Mild degradation was observed in acidic and oxidative conditions. Escitalopram oxalate was stable to neutral, photolytic, and thermal stress. Successful separation of the drug from degradation products formed under stress conditions was achieved on a PerfectSil-100 ODS-3 column [C18 (5 microm, 25 cm x 4.6 mm id)] using methanol-0.01 M acetate buffer pH 3.8 adjusted with acetic acid (45 + 55) as the mobile phase. The flow rate was 1 ml/min, and the detection wavelength was 239 nm. The method was validated according to ICH guidelines. Major degradation products formed in hydrolysis and oxidative conditions were isolated, and structural elucidation of degradation products was done by LCIMS and infrared spectrometry studies. The major hydrolysis degradation product was confirmed as 1-(3-dimethylaminopropyl)-1-(4-fluoro- phenyl)-1,3dihydroisobenzofuran-5-carboxylic acid, and the major oxidative degradation product was confirmed as 1-{[3-dimethylamino(oxide)- propyl]-1-(4-fluro-phenyl)}-1,3-dihydro-isobenzofuran- 5-carbonitrile.

  17. Photodegradation of Orange II using waste paper sludge-derived heterogeneous catalyst in the presence of oxalate under ultraviolet light emitting diode irradiation.

    PubMed

    Zhou, Guoqiang; Guo, Jinyi; Zhou, Guowang; Wan, Xiankai; Shi, Huixiang

    2016-09-01

    A waste paper sludge-derived heterogeneous catalyst (WPS-Fe-350) was synthesized via a facile method and successfully applied for the degradation of Orange II in the presence of oxalic acid under the illumination of ultraviolet light emitting diode (UV-LED) Powder X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electronic microscopy and N2 sorption isotherm analysis indicated the formation of α-Fe2O3 in the mesoporous nanocomposite. The degradation test showed that WPS-Fe-350 exhibited rapid Orange II (OII) degradation and mineralization in the presence of oxalic acid under the illumination of UV-LED. The effects of pH, oxalic acid concentration and dosage of the catalyst on the degradation of OII were evaluated, respectively. Under the optimal conditions (1g/L catalyst dosage, 2mmol/L oxalic acid and pH3.0), the degradation percentage for a solution containing 30mg/L OII reached 83.4% under illumination by UV-LED for 80min. Moreover, five cyclic tests for OII degradation suggested that WPS-Fe-350 exhibited excellent stability of catalytic activity. Hence, this study provides an alternative environmentally friendly way to reuse waste paper sludge and an effective and economically viable method for degradation of azo dyes and other refractory organic pollutants in water. PMID:27593273

  18. Photodegradation of Orange II using waste paper sludge-derived heterogeneous catalyst in the presence of oxalate under ultraviolet light emitting diode irradiation.

    PubMed

    Zhou, Guoqiang; Guo, Jinyi; Zhou, Guowang; Wan, Xiankai; Shi, Huixiang

    2016-09-01

    A waste paper sludge-derived heterogeneous catalyst (WPS-Fe-350) was synthesized via a facile method and successfully applied for the degradation of Orange II in the presence of oxalic acid under the illumination of ultraviolet light emitting diode (UV-LED) Powder X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electronic microscopy and N2 sorption isotherm analysis indicated the formation of α-Fe2O3 in the mesoporous nanocomposite. The degradation test showed that WPS-Fe-350 exhibited rapid Orange II (OII) degradation and mineralization in the presence of oxalic acid under the illumination of UV-LED. The effects of pH, oxalic acid concentration and dosage of the catalyst on the degradation of OII were evaluated, respectively. Under the optimal conditions (1g/L catalyst dosage, 2mmol/L oxalic acid and pH3.0), the degradation percentage for a solution containing 30mg/L OII reached 83.4% under illumination by UV-LED for 80min. Moreover, five cyclic tests for OII degradation suggested that WPS-Fe-350 exhibited excellent stability of catalytic activity. Hence, this study provides an alternative environmentally friendly way to reuse waste paper sludge and an effective and economically viable method for degradation of azo dyes and other refractory organic pollutants in water.

  19. Characterization of wheat germin (oxalate oxidase) expressed by Pichia pastoris

    SciTech Connect

    Pan, Heng-Yen; Whittaker, Mei M.; Bouveret, Romaric; Berna, Anne; Bernier, Francois; Whittaker, James W. . E-mail: jim@ebs.ogi.edu

    2007-05-18

    High-level secretory expression of wheat (Triticum aestivum) germin/oxalate oxidase was achieved in Pichia pastoris fermentation cultures as an {alpha}-mating factor signal peptide fusion, based on the native wheat cDNA coding sequence. The oxalate oxidase activity of the recombinant enzyme is substantially increased (7-fold) by treatment with sodium periodate, followed by ascorbate reduction. Using these methods, approximately 1 g (4 x 10{sup 4} U) of purified, activated enzyme was obtained following eight days of induction of a high density Pichia fermentation culture, demonstrating suitability for large-scale production of oxalate oxidase for biotechnological applications. Characterization of the recombinant protein shows that it is glycosylated, with N-linked glycan attached at Asn47. For potential biomedical applications, a nonglycosylated (S49A) variant was also prepared which retains essentially full enzyme activity, but exhibits altered protein-protein interactions.

  20. The influence of scale inhibitors on calcium oxalate

    SciTech Connect

    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. 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.

  1. 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.

  2. The Path of Carbon in Photosynthesis VIII. The Role of Malic Acid

    DOE R&D Accomplishments Database

    Bassham, James A.; Benson, Andrew A.; Calvin, Melvin

    1950-01-25

    Malonate has been found to inhibit the formation of malic acid during short periods of photosynthesis with radioactive carbon dioxide. This result, together with studies which show the photosynthetic cycle to be operating normally at the same time, indicates that malic acid is not an intermediate in photosynthesis but is probably closely related to some intermediate of the cycle. Absence of labeled succinic and fumaric acids in these experiments, in addition to the failure of malonate to inhibit photosynthesis, precludes the participation of these acids as intermediates in photosynthesis.

  3. Trans-hemispheric contribution of C2-C10 α, ω-dicarboxylic acids, and related polar compounds to water-soluble organic carbon in the western Pacific aerosols in relation to photochemical oxidation reactions

    NASA Astrophysics Data System (ADS)

    SempéRé, Richard; Kawamura, Kimitaka

    2003-06-01

    Marine aerosol samples were collected during a western Pacific cruise covering the latitude range between 35°N and 40°S (140°E-180°E). They were analyzed for total carbon (TC), total nitrogen (TN), water-soluble organic carbon (WSOC) along with the molecular distributions of C2-C10 α, ω-dicarboxylic acids, and related polar compounds, mainly, ω-oxocarboxylic acids (C2-C9) and α-dicarbonyls (C2-C3). Oxalic acid (C2) was the most abundant followed by malonic (C3) and succinic (C4) acids. The total diacid concentration range was 7-605 ng m-3 (av. 85 ng m-3) and the diacid-carbon accounted for 2-15% (average 8%) of WSOC which comprised 29-55% (average 40%) of TC. Dry depositions of total diacids over the northern and southern Pacific Ocean were estimated to be 256-1907 μg m-2 yr-1 (average 735; n = 4) and 22-396 μg m-2 yr-1 (average 134; n = 14), respectively, whereas the air-to-sea flux of oxalic acid was 18-1351 μg m-2 yr-1 (average 466 μg m-2 yr-1) and 7.5-275 μg m-2 yr-1 (average 75 μg m-2 yr-1) in the Northern and Southern Hemispheres. We observed that the concentration ratios of diacid-C/WSOC, azelaic acid (C9)/ω-oxononanoic acid, maleic acid (iC4cis)/fumaric (iC4trans) acid and succinic acid (C4)/total diacids were correlated with air temperature. These findings showed that the intensity of photochemical oxidation reactions and thus the variation in sunlight intensity characterized here by air temperature, significantly control the molecular distribution of water-soluble organic compounds during the long-range transport of anthropogenic and/or biogenic higher molecular weight organic compounds.

  4. Molecular composition of dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls and fatty acids in atmospheric aerosols from Tanzania, East Africa during wet and dry seasons

    NASA Astrophysics Data System (ADS)

    Mkoma, S. L.; Kawamura, K.

    2013-02-01

    Atmospheric aerosol samples of PM2.5 and PM10 were collected during the wet and dry seasons in 2011 from a rural site in Tanzania and analysed for water-soluble dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, and fatty acids using a gas chromatography/flame ionization detector (GC/FID) and GC/mass spectrometry. Here we report the molecular composition and sources of diacids and related compounds for wet and dry seasons. Oxalic acid (C2) was found as the most abundant diacid species followed by succinic and/or malonic acids whereas glyoxylic acid and glyoxal were the dominant ketoacid and α-dicarbonyl, respectively in both seasons in PM2.5 and PM10. Mean concentration of C2 in PM2.5 (121 ± 47 ng m-3) was lower in wet season than dry season (258 ± 69 ng m-3). Similarly, PM10 samples showed lower concentration of C2 (169 ± 42 ng m-3) in wet season than dry season (292 ± 165 ng m-3). Relative abundances of C2 in total diacids were 65% and 67% in PM2.5 and 65% and 64% in PM10 in the wet and dry seasons, respectively. Total concentrations of diacids (289-362 ng m-3), ketoacids (37.8-53.7 ng m-3), and α-dicarbonyls (5.7-7.8 ng m-3) in Tanzania are higher than those reported at a rural background site in Nylsvley (South Africa) but comparable or lower than those reported from sites in Asia and Europe. Diacids and ketoacids were found to be present mainly in PM2.5 in both seasons (total α-dicarbonyls in the dry season), suggesting a production of organic acids from pyrogenic sources and photochemical oxidations. Averaged contributions of total diacids to aerosol total carbon were 1.4% in PM2.5 and 2.1% in PM10 during wet season and 3.3% in PM2.5 and 3.9% in PM10 during dry season whereas those to water-soluble organic carbon were 2.2% and 4.7% in PM2.5 during wet season and 3.1% and 5.8% in PM10 during dry season. The higher ratios in dry season suggest an enhanced photochemical oxidation of organic precursors probably via heterogeneous reactions on

  5. High Temperature Raman Spectroscopy Study of the Conversion of Formate into Oxalate: Search for the Elusive CO 2 2 - Intermediate

    NASA Astrophysics Data System (ADS)

    Ryan, Charles; Mead, Anna; Lakkaraju, Prasad; Kaczur, Jerry; Bennett, Christopher; Dobbins, Tabbetha

    Research on conversion of carbon dioxide into chemicals and fuels has the potential to address three problems of global relevance. (a) By removing carbon dioxide from the atmosphere, we are able to reduce the amount of greenhouse gases in the atmosphere, (b) by converting carbon dioxide into fuels, we are providing pathways for renewable energy sources, (c) by converting carbon dioxide into C2 and higher order compounds, and we are able to generate valuable precursors for organic synthesis. Formate salts are formed by the electrochemical reduction of carbon dioxide in aqueous media. However, in order to increase the utilization of carbon dioxide, methods need to be developed for the conversion of formate into compounds containing two carbon atoms such as oxalate or oxalic acid. Recently, we examined the thermal conversion of sodium formate into sodium oxalate utilizing a hydride ion catalyst. The proposed mechanism for this reaction involves the carbon dioxide dianion. Currently at NASA Goddard Space Flight Center.

  6. Biomimetic growth of calcium oxalate crystals: synchrotron X-ray studies

    NASA Astrophysics Data System (ADS)

    Uysal, Ahmet; Stripe, Benjamin; Dutta, Pulak

    2010-03-01

    Oriented crystals of calcium oxalate monohydrate (COM) form one of the major constituents of kidney stones in humans, and these crystals are also found in many plants. It is widely accepted that an organic matrix of lipids and proteins is involved in the crystallization of COM, though their role is not well-understood [1]. Langmuir monolayers of lipids on supersaturated aqueous solutions can be used to mimic the lipid-crystal interface during mineralization. We have studied nucleation and growth of COM crystals under heneicosanoic acid monolayers at the air-water interface. We used synchrotron x-rays in the grazing incidence geometry to determine the structure of the organic monolayer and the orientation of COM crystals in-situ during crystallization. We see that the (-101) faces of COM crystals are parallel to the organic matrix. There is a commensurate relationship between the heneicosanoic acid monolayer and the (-101) crystal face that may be responsible from the oriented growth. Evolution of the monolayer structure with time will be described. [1]S. R. Khan, Calcium Oxalate in Biological Systems, CRC Press, Boca Raton, 1995

  7. Enzymatic hydrolysis of phytate and effects on soluble oxalate concentration in foods.

    PubMed

    Israr, Beenish; Frazier, Richard A; Gordon, Michael H

    2017-01-01

    Soluble oxalate in foods is major concern for kidney stone formers due to its tendency to increase urinary oxalate concentration. Phytate forms complexes with cations, which increases soluble oxalate by making cations unavailable to precipitate oxalate. Thus, in order to reduce soluble oxalate, bran samples (wheat, oat and barley) and bean samples (red kidney bean and white bean) were treated with phytase. Release of phosphate after phytate degradation and its association with calcium was determined. Phosphate concentration increased after application of phytase in all samples, but effect on soluble oxalate concentration varied. Wheat and oat bran showed significant reduction (P<0.05) in soluble oxalate compared to bean samples. Wheat bran, oat bran and white bean had a lower calcium:phosphate ratio than barley bran and red kidney beans. Correlation of the calcium:phosphate molar ratio with release of phosphate depends on concentration of calcium ions and this influences soluble oxalate concentration. PMID:27507467

  8. Enzymatic hydrolysis of phytate and effects on soluble oxalate concentration in foods.

    PubMed

    Israr, Beenish; Frazier, Richard A; Gordon, Michael H

    2017-01-01

    Soluble oxalate in foods is major concern for kidney stone formers due to its tendency to increase urinary oxalate concentration. Phytate forms complexes with cations, which increases soluble oxalate by making cations unavailable to precipitate oxalate. Thus, in order to reduce soluble oxalate, bran samples (wheat, oat and barley) and bean samples (red kidney bean and white bean) were treated with phytase. Release of phosphate after phytate degradation and its association with calcium was determined. Phosphate concentration increased after application of phytase in all samples, but effect on soluble oxalate concentration varied. Wheat and oat bran showed significant reduction (P<0.05) in soluble oxalate compared to bean samples. Wheat bran, oat bran and white bean had a lower calcium:phosphate ratio than barley bran and red kidney beans. Correlation of the calcium:phosphate molar ratio with release of phosphate depends on concentration of calcium ions and this influences soluble oxalate concentration.

  9. High abundances of water-soluble dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the mountaintop aerosols over the North China Plain during wheat burning season

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Tachibana, E.; Okuzawa, K.; Aggarwal, S. G.; Kanaya, Y.; Wang, Z. F.

    2013-08-01

    Aerosol (TSP) samples were collected at the summit of Mount Tai (elevation: 1534 m a.s.l., 36.25° N, 117.10° E) located in the North China Plain using a high-volume air sampler and pre-combusted quartz filters. Sampling was conducted on day/night or 3 h basis in the period from 29 May to 28 June 2006 during the field burning of wheat straw residue and the post-burning season. The filter samples were analyzed for low-molecular-weight dicarboxylic acids, ketoacids and α-dicarbonyls using capillary gas chromatography (GC) and GC-MS employing water extraction and butyl ester derivatization. Molecular distributions of dicarboxylic acids (C2-C11, 220-6070 ng m-3) were characterized by a predominance of oxalic (C2) acid (105-3920 ng m-3) followed by succinic (C4) or malonic (C3) acid. Unsaturated aliphatic diacids, including maleic (M), isomaleic (iM) and fumaric (F) acids, were also detected together with aromatic diacids (phthalic, isophthalic and terephthalic acids). ω-oxocarboxylic acids (C2-C9, 24-610 ng m-3) were detected as the second most abundant compound class with the predominance of glyoxylic acid (11-360 ng m-3), followed by α-ketoacid (pyruvic acid, 3-140 ng m-3) and α-dicarbonyls (glyoxal, 1-230 ng m-3 and methylglyoxal, 2-120 ng m-3). We found that these levels (>6000 ng m-3 for diacids) are several times higher than those reported in Chinese megacities at ground levels. The concentrations of diacids increased from late May to early June, showing a maximum on 7 June, and then significantly decreased during the period 8-11 June, when the wind direction shifted from southerly to northerly. Similar temporal trends were found for ketocarboxylic acids and α-dicarbonyls as well as total carbon (TC) and water-soluble organic carbon (WSOC). The temporal variations of water-soluble organics were interpreted by the direct emission from the field burning of agricultural wastes (wheat straw) in the North China Plain and the subsequent photochemical oxidation of

  10. Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate

    NASA Technical Reports Server (NTRS)

    McCollom, T. M.; Simoneit, B. R.

    1999-01-01

    The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

  11. Desorption of Mercury(II) on Kaolinite in the Presence of Oxalate or Cysteine

    SciTech Connect

    Senevirathna, W. U.; Zhang, Hong; Gu, Baohua

    2011-01-01

    Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio- uptake of Hg in aquatic systems. We studied the desorption of Hg(II) on kaolinite in the presence of oxalate or cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, 7), ligand concentration (0.25, 1.0 mM), and temperature (15, 25, 35 C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH-dependant. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed at pH 3 within 2 h, compared to <10% at pH 7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80 min with the desorption less than 20%, but it appeared to enhance the Hg(II) desorption afterwards. The effect of ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particles and in the solution probably can also affect the Hg(II) desorption.

  12. 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…

  13. In female rats, ethylene glycol treatment elevates protein expression of hepatic and renal oxalate transporter sat-1 (Slc26a1) without inducing hyperoxaluria

    PubMed Central

    Breljak, Davorka; Brzica, Hrvoje; Vrhovac, Ivana; Micek, Vedran; Karaica, Dean; Ljubojević, Marija; Sekovanić, Ankica; Jurasović, Jasna; Rašić, Dubravka; Peraica, Maja; Lovrić, Mila; Schnedler, Nina; Henjakovic, Maja; Wegner, Waja; Burckhardt, Gerhard; Burckhardt, Birgitta C.; Sabolić, Ivan

    2015-01-01

    Aim To investigate whether the sex-dependent expression of hepatic and renal oxalate transporter sat-1 (Slc26a1) changes in a rat model of ethylene glycol (EG)-induced hyperoxaluria. Methods Rats were given tap water (12 males and 12 females; controls) or EG (12 males and 12 females; 0.75% v/v in tap water) for one month. Oxaluric state was confirmed by biochemical parameters in blood plasma, urine, and tissues. Expression of sat-1 and rate-limiting enzymes of oxalate synthesis, alcohol dehydrogenase 1 (Adh1) and hydroxy-acid oxidase 1 (Hao1), was determined by immunocytochemistry (protein) and/or real time reverse transcription polymerase chain reaction (mRNA). Results EG-treated males had significantly higher (in μmol/L; mean ± standard deviation) plasma (59.7 ± 27.2 vs 12.9 ± 4.1, P < 0.001) and urine (3716 ± 1726 vs 241 ± 204, P < 0.001) oxalate levels, and more abundant oxalate crystaluria than controls, while the liver and kidney sat-1 protein and mRNA expression did not differ significantly between these groups. EG-treated females, in comparison with controls had significantly higher (in μmol/L) serum oxalate levels (18.8 ± 2.9 vs 11.6 ± 4.9, P < 0.001), unchanged urine oxalate levels, low oxalate crystaluria, and significantly higher expression (in relative fluorescence units) of the liver (1.59 ± 0.61 vs 0.56 ± 0.39, P = 0.006) and kidney (1.77 ± 0.42 vs 0.69 ± 0.27, P < 0.001) sat-1 protein, but not mRNA. The mRNA expression of Adh1 was female-dominant and that of Hao1 male-dominant, but both were unaffected by EG treatment. Conclusions An increased expression of hepatic and renal oxalate transporting protein sat-1 in EG-treated female rats could protect from hyperoxaluria and oxalate urolithiasis. PMID:26526882

  14. Oxalate Nephropathy After Continuous Infusion of High-Dose Vitamin C as an Adjunct to Burn Resuscitation

    PubMed Central

    Pamplin, Jeremy; Studer, Lynette; Hughes, Rhome L.; King, Booker T.; Graybill, John C.; Chung, Kevin K.

    2016-01-01

    Fluid resuscitation is the foundation of management in burn patients and is the topic of considerable research. One adjunct in burn resuscitation is continuous, high-dose vitamin C (ascorbic acid) infusion, which may reduce fluid requirements and thus decrease the risk for over resuscitation. Research in preclinical studies and clinical trials has shown continuous infusions of high-dose vitamin C to be beneficial with decrease in resuscitative volumes and limited adverse effects. However, high-dose and low-dose vitamin C supplementation has been shown to cause secondary calcium oxalate nephropathy, worsen acute kidney injury, and delay renal recovery in non-burn patients. To the best of our knowledge, the authors present the first case series in burn patients in whom calcium oxalate nephropathy has been identified after high-dose vitamin C therapy. PMID:25812044

  15. Synthesis and structures of new uranyl malonate complexes with carbamide derivatives

    SciTech Connect

    Serezhkina, L. B.; Grigor’ev, M. S.; Medvedkov, Ya. A.; Serezhkin, V. N.

    2015-09-15

    Crystals of new malonate-containing uranyl complexes [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Imon)(H{sub 2}O)] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O4)(Meur){sub 3}] (II), where Imon is imidazolidin-2-one (ethylenecarbamide) and Meur is methyl-carbamide, have been synthesized and studied by X-ray diffraction. Both compounds crystallize in the monoclinic system with the following unit-cell parameters (at 100 K): a = 11.1147(10) Å, b = 6.9900(6) Å, c = 14.4934(12) Å, β = 92.042(2)°, V = 1125.30(17) Å{sup 3}, sp. gr. P2{sub 1}/n, Z = 4, R{sub 1} = 0.0398 (I); a = 16.6613(5) Å, b = 9.5635(3) Å, c = 22.9773(6) Å, β = 103.669(2)°, V = 3557.51(18) Å{sup 3}, sp. gr. C2/c, Z = 8, R{sub 1} = 0.0207 (II). The crystals are composed of electroneutral chains [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Imon)(H{sub 2}O)] and mononuclear groups [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Meur){sub 3}] as the structural units belonging to the crystal-chemical groups AT{sup 11}M{sub 2}{sup 1} and AB{sup 01}M{sub 3}{sup 1} (A =UO{sub 2}{sup 2+}, T{sup 11} and B{sup 01} = C{sub 3}H{sub 2}, M{sup 1} = Imon, H{sub 2}O, or Meur), respectively, of uranyl complexes. The packing modes of the uranyl-containing complexes were analyzed by the method of molecular Voronoi—Dirichlet polyhedra.

  16. High abundances of water-soluble dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the mountain aerosols over the North China Plain during wheat burning season

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Tachibana, E.; Okuzawa, K.; Aggarwal, S. G.; Kanaya, Y.; Wang, Z. F.

    2013-02-01

    Aerosol (TSP) samples were collected at the summit of Mount Tai (elevation: 1534 m a.s.l., 36.25° N; 117.10° E) located in the North China Plain using a high-volume air sampler and pre-combusted quartz filters. Sampling was conducted on day/night or 3 h basis in the period from 29 May to 28 June 2006 during the field burning of wheat straw residue and the post-burning season. The filter samples were analyzed for low molecular weight dicarboxylic acids, ketoacids and α-dicarbonyls using capillary gas chromatography (GC) and GC-MS employing water extraction and butyl ester derivatization. Dicarboxylic acids (C2-C11, 220-6070 ng m-3) were characterized by a predominance of oxalic (C2) acid (105-3920 ng m-3) followed by succinic (C4) or malonic (C3) acid. Unsaturated aliphatic diacids, including maleic (M), isomaleic (iM) and fumaric (F) acid, were also detected together with aromatic diacids (phthalic, iso-phthalic and tere-phthalic acids). ω-Oxocarboxylic acids (C2-C9, 24-610 ng m-3) were detected as the second most abundant compound class with the predominance of glyoxylic acid (11-360 ng m-3), followed by α-ketoacid (pyruvic acid, 3-140 ng m-3) and α-dicarbonyls (glyoxal, 1-230 ng m-3 and methylglyoxal, 2-120 ng m-3). We found that these levels (> 6000 ng m-3 for diacids) are several times higher than those reported in Chinese megacities at ground levels. The concentrations of diacids increased from late May to early June showing a maximum on 7 June and then significantly decreased during 8-11 June when the wind direction shifted from northeasterly to northerly. Similar temporal trends were found for ketocarboxylic acids and α-dicarbonyls as well as total carbon (TC) and water-soluble organic carbon (WSOC). The temporal variations of water-soluble organics were interpreted by the direct emission from the field burning products of agricultural wastes (wheat straw) in the North China Plain and the subsequent photochemical oxidation of volatile and semi

  17. Production of battery grade materials via an oxalate method

    SciTech Connect

    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.

  18. Acute Oxalate Nephropathy following Ingestion of Averrhoa bilimbi Juice

    PubMed Central

    George, Jacob; Kumar, Sajeev; Gracious, Noble

    2014-01-01

    Plant toxins are known to cause acute kidney injury in tropical countries. We report two cases of acute kidney injury with tubular oxalate deposition following ingestion of Averrhoa bilimbi fruit juice. Both patients had complete renal recovery though one required dialytic support. PMID:24995136

  19. Formation of solid solutions between racemic and enantiomeric citalopram oxalate.

    PubMed

    de Diego, Heidi Lopez; Bond, Andrew D; Dancer, Robert James

    2011-05-01

    The X-ray powder diffractograms of racemic citalopram oxalate and (S)-citalopram oxalate are very similar, but the melting point of the racemate is higher than that of the pure enantiomer. The higher melting point indicates that the racemate is a racemic compound, rather than a conglomerate. The crystal structure of the enantiomer contains two molecules of (S)-citalopram in the asymmetric unit. The conformation of the two molecules is different but they approximate mirror images of each other if the aromatic groups are interchanged. The crystal structure of the racemate is essentially isostructural with that of the enantiomer, having almost the same cell parameters but containing a crystallographic inversion centre that is not retained in the enantiomer structure. The closely-comparable crystal structures permit solid solutions to be formed between racemic and enantiomeric citalopram oxalate. Phase diagrams of the (R)-citalopram and (S)-citalopram oxalate system are constructed, and they show that solid solutions are formed at all ratios of the two enantiomers.

  20. Oxalate absorption and postprandial urine supersaturation in an experimental human model of absorptive hypercalciuria.

    PubMed

    Erickson, S B; Cooper, K; Broadus, A E; Smith, L H; Werness, P G; Binder, H J; Dobbins, J W

    1984-07-01

    The effect of 1.25-dihydroxyvitamin D [1,25-(OH)2D] on dietary oxalate absorption and postprandial urine supersaturation with calcium oxalate was determined in 11 normal subjects. 1,25-(OH)2D increased the urinary excretion of orally administered [14C]oxalate in the 8 h period after a liquid meal containing 1.875 mmol of calcium and 0.83 mmol of oxalate (P less than 0.01), and during a 48 h period when the subjects ingested a diet containing 25 mmol of calcium and 3.3 mmol of oxalate/day (P less than 0.01); however, 1,25-(OH)2D administration had no effect on [14C]oxalate excretion when calcium was removed from the liquid meal. 1.25-(OH)2D increased 24 h urinary oxalate excretion from 28.7 +/- 2.1 mmol/mol of creatinine to 36.8 +/- 2.6 mmol/mol of creatinine (P less than 0.05) on the 10 mmol/day calcium diet and from 26.4 +/- 2.9 to 33.2 +/- 2.2 mmol/mol of creatinine (P less than 0.1) on the 25 mmol/day calcium diet. A linear correlation (r = 0.72) was found between plasma 1,25-(OH)2D levels and urinary [14C]oxalate excretion after the liquid meal. 1,25-(OH)2D administration produced postprandial supersaturation of urine with calcium oxalate and calcium oxalate crystalluria. These studies suggest that 1,25-(OH)2D increases oxalate absorption (and urinary excretion) by increasing calcium absorption, which results in less binding of calcium to oxalate in the intestine; therefore more oxalate is available for absorption. The combined effect of increased calcium and oxalate absorption results in postprandial supersaturation of urine with calcium oxalate, with resultant crystalluria. PMID:6547378

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

    PubMed

    Freel, Robert W; Whittamore, Jonathan M; Hatch, Marguerite

    2013-10-01

    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.

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

    SciTech Connect

    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 test 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 the

  3. Efficient Synthesis of Chiral Trisubstituted 1,2-Allenyl Ketones by Catalytic Asymmetric Conjugate Addition of Malonic Esters to Enynes.

    PubMed

    Yao, Qian; Liao, Yuting; Lin, Lili; Lin, Xiaobin; Ji, Jie; Liu, Xiaohua; Feng, Xiaoming

    2016-01-26

    An N,N'-dioxide/scandium(III) complex catalyzed, highly efficient conjugate addition of malonic esters to enynes is described. A range of trisubstituted 1,2-allenyl ketones were obtained in high yields (up to 99 %) with good d.r. (up to 95/5) and excellent ee values (97 %-99 %). Moreover, the products could be easily transformed into chiral furan and 5-hydroxypyrazoline derivatives, both of which are important skeletons of many biologically active compounds and pharmacologicals. PMID:26694204

  4. Oxalate secretion by ectomycorrhizal Paxillus involutus is mineral-specific and controls calcium weathering from minerals.

    PubMed

    Schmalenberger, A; Duran, A L; Bray, A W; Bridge, J; Bonneville, S; Benning, L G; Romero-Gonzalez, M E; Leake, J R; Banwart, S A

    2015-01-01

    Trees and their associated rhizosphere organisms play a major role in mineral weathering driving calcium fluxes from the continents to the oceans that ultimately control long-term atmospheric CO2 and climate through the geochemical carbon cycle. Photosynthate allocation to tree roots and their mycorrhizal fungi is hypothesized to fuel the active secretion of protons and organic chelators that enhance calcium dissolution at fungal-mineral interfaces. This was tested using (14)CO2 supplied to shoots of Pinus sylvestris ectomycorrhizal with the widespread fungus Paxillus involutus in monoxenic microcosms, revealing preferential allocation by the fungus of plant photoassimilate to weather grains of limestone and silicates each with a combined calcium and magnesium content of over 10 wt.%. Hyphae had acidic surfaces and linear accumulation of weathered calcium with secreted oxalate, increasing significantly in sequence: quartz, granite < basalt, olivine, limestone < gabbro. These findings confirmed the role of mineral-specific oxalate exudation in ectomycorrhizal weathering to dissolve calcium bearing minerals, thus contributing to the geochemical carbon cycle. PMID:26197714

  5. [Components of Urinary Nanocrystals and Their Influence on Formation of Calcium Oxalate Stones].

    PubMed

    Li, Yu-bao; Wen, Xiao-ling; Xue, Jun-fa; Ouyang, Jian-ming

    2015-08-01

    High-resolution transmission electron microscopy, X-ray diffraction, selected area electron diffraction (SAED), and energy dispersive spectroscopy (EDS) were accurately performed to analyze the components of nanocrystals in the urine of patients with calcium oxalate (CaOx) stones. XRD, SAED and FFT detected the presence of calcium oxalate monohydrate (COM), uric acid (UA), and calcium phosphate (CaP). EDS detected the elements of C, O, Ca, with a small amount of N and P. These results showed that the main components of urinary nanocrystals were COM, with a small amount UA and phosphate. HRTEM observation showed that the particle size of urinary nanocrystals was dozens of nanometers. The result was consistent with the calculation by Debye-Scherrer equation. When the urine was filtered through a microporous membrane of 0.45, 1.2, and 3 μm, respectively, the number of diffraction peaks of the obtained urine crystallites increased with the increased pore size, indicating the increase of urinary crystallite species. Crystal nucleation, growth, aggregation, and adhesion of crystals to the renal epithelial cells are important processes for CaOx stone formation. The presence of a large amount of COM crystals in patients' urine is a critical factor for CaOx stones formation. Nano UA and CaP crystallite can induce the CaOx stone formation as central nidus.

  6. Oxalate secretion by ectomycorrhizal Paxillus involutus is mineral-specific and controls calcium weathering from minerals

    PubMed Central

    Schmalenberger, A.; Duran, A. L.; Bray, A. W.; Bridge, J.; Bonneville, S.; Benning, L. G.; Romero-Gonzalez, M. E.; Leake, J. R.; Banwart, S. A.

    2015-01-01

    Trees and their associated rhizosphere organisms play a major role in mineral weathering driving calcium fluxes from the continents to the oceans that ultimately control long-term atmospheric CO2 and climate through the geochemical carbon cycle. Photosynthate allocation to tree roots and their mycorrhizal fungi is hypothesized to fuel the active secretion of protons and organic chelators that enhance calcium dissolution at fungal-mineral interfaces. This was tested using 14CO2 supplied to shoots of Pinus sylvestris ectomycorrhizal with the widespread fungus Paxillus involutus in monoxenic microcosms, revealing preferential allocation by the fungus of plant photoassimilate to weather grains of limestone and silicates each with a combined calcium and magnesium content of over 10 wt.%. Hyphae had acidic surfaces and linear accumulation of weathered calcium with secreted oxalate, increasing significantly in sequence: quartz, granite < basalt, olivine, limestone < gabbro. These findings confirmed the role of mineral-specific oxalate exudation in ectomycorrhizal weathering to dissolve calcium bearing minerals, thus contributing to the geochemical carbon cycle. PMID:26197714

  7. Oxalate secretion by ectomycorrhizal Paxillus involutus is mineral-specific and controls calcium weathering from minerals.

    PubMed

    Schmalenberger, A; Duran, A L; Bray, A W; Bridge, J; Bonneville, S; Benning, L G; Romero-Gonzalez, M E; Leake, J R; Banwart, S A

    2015-07-22

    Trees and their associated rhizosphere organisms play a major role in mineral weathering driving calcium fluxes from the continents to the oceans that ultimately control long-term atmospheric CO2 and climate through the geochemical carbon cycle. Photosynthate allocation to tree roots and their mycorrhizal fungi is hypothesized to fuel the active secretion of protons and organic chelators that enhance calcium dissolution at fungal-mineral interfaces. This was tested using (14)CO2 supplied to shoots of Pinus sylvestris ectomycorrhizal with the widespread fungus Paxillus involutus in monoxenic microcosms, revealing preferential allocation by the fungus of plant photoassimilate to weather grains of limestone and silicates each with a combined calcium and magnesium content of over 10 wt.%. Hyphae had acidic surfaces and linear accumulation of weathered calcium with secreted oxalate, increasing significantly in sequence: quartz, granite < basalt, olivine, limestone < gabbro. These findings confirmed the role of mineral-specific oxalate exudation in ectomycorrhizal weathering to dissolve calcium bearing minerals, thus contributing to the geochemical carbon cycle.

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

    PubMed

    Calla, Bernarda; Blahut-Beatty, Laureen; Koziol, Lisa; Zhang, Yunfang; Neece, David J; Carbajulca, Doris; Garcia, Alexandre; Simmonds, Daina H; Clough, Steven J

    2014-08-01

    Oxalate oxidases (OxO) catalyse the degradation of oxalic acid (OA). Highly resistant transgenic soybean carrying an 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 Sclerotinia sclerotiorum using soybean cDNA microarrays. The genes with changed expression at statistically significant levels (overall F-test P-value cut-off of 0.0001) were classified into functional categories and pathways, and were analysed to evaluate the differences in transcriptome profiles. Although many genes and pathways were found to be similarly activated or repressed in both genotypes after inoculation with S. sclerotiorum, the OxO genotype displayed a measurably faster induction of basal defence responses, as observed by the differential changes in defence-related and secondary metabolite genes compared with its susceptible parent AC Colibri. In addition, the experiment presented provides data on several other transcripts that support the hypothesis that S. sclerotiorum at least partially elicits the hypersensitive response, induces lignin synthesis (cinnamoyl CoA reductase) and elicits as yet unstudied signalling pathways (G-protein-coupled receptor and related). Of the nine genes showing the most extreme opposite directions of expression between genotypes, eight were related to photosynthesis and/or oxidation, highlighting the importance of redox in the control of this pathogen.

  9. Oxalate content of soybean seeds (Glycine max: Leguminosae), soyfoods, and other edible legumes.

    PubMed

    Massey, L K; Palmer, R G; Horner, H T

    2001-09-01

    Consumption of soybeans and food products made from them is increasing because of their desirable nutritional value. However, the oxalate content of seeds from 11 cultivars of soybean showed relatively high levels of total oxalate from 0.67 to 3.5 g/100 g of dry weight. Oxalate primarily was found as calcium oxalate crystals. Thirteen tested commercial soyfoods contained between 16 and 638 mg of total oxalate per serving. These values compare to those of three other legume foods, peanut butter, refried beans, and lentils, which contained 197, 193, and 100 mg of total oxalate per serving, respectively. After oxalate has been absorbed from the diet, it cannot be metabolized and is excreted by the kidney into urine, where it binds to calcium forming an insoluble salt that may precipitate to form kidney stones. The amounts of total oxalate in soybean seeds, soy foods, and other common legume foods exceed current recommendations for oxalate consumption by individuals who have a history of calcium oxalate kidney/urinary stones. This study serves as the basis to find soybean cultivars lower in oxalate, which will have lower risk for kidney stone formation after human consumption. PMID:11559120

  10. 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.

  11. 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