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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

    PubMed Central

    2012-01-01

    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.) PMID:22515214

  2. Oxalic acid poisoning

    MedlinePlus

    Symptoms of oxalic acid poisoning include: Abdominal pain Burns and blisters where the acid contacted the skin Collapse Convulsions Mouth pain Shock Throat pain Tremors (unintentional trembling) Vomiting

  3. Distinct effects of oxalate versus malonate on the iron redox chemistry: Implications for the photo-Fenton reaction.

    PubMed

    Xiao, Dongxue; Guo, Yaoguang; Lou, Xiaoyi; Fang, Changling; Wang, Zhaohui; Liu, Jianshe

    2014-05-01

    The dicarboxylic acids oxalate (Oxal) and malonate (Mal) are frequently detected as the final low-molecular-weight organic acids during oxidative degradation of aromatic compounds. Here a distinct effect of Oxal versus Mal on iron-based photocatalytic technologies was reported by testing the degradation efficiency of the dye rhodamine B. The rates of dye degradation in irradiated Fe(III) solutions depended on Fe(III/II) speciation, photoreactivities of Fe complexes and reactivities of Fe(II) complexes with H2O2. Photolysis of the Fe(III)-oxalato complex was favorable due to the formation of O2-, HO2 and OH for oxidizing the dye; however, an excess of H2O2 could quench the excited state of ferrioxalate, decreasing the degradation efficiency. In contrast, activities of UV/Fe(III) in the presence of Mal were significantly diminished because Fe(III)-Mal complexes, with much lower quantum yield of Fe(II) from photoreduction, dominated Fe(III) speciation. The results provide data for an understanding of the mechanism of iron redox (photo)chemistry mediated by diacids, which will aid in selecting appropriate Fe ligands, screening photo-Fenton conditions and designing UV/Fe(III) treatability. PMID:24359921

  4. Malonic acid: A potential reagent in decontamination processes for Ni-rich alloy surfaces

    NASA Astrophysics Data System (ADS)

    García, D.; Bruyère, V. I. E.; Bordoni, R.; Olmedo, A. M.; Morando, P. J.

    2011-05-01

    The ability of malonic acid as a dissolution agent toward synthetic Ni ferrite and Alloy 600 and 800 corrosion products was explored. Its performance in the dissolution kinetics of Ni ferrite powders was compared with the one of oxalic acid. Kinetic parameters were obtained and the dependency on external Fe(II) was modelled. Oxidized samples used in descaling tests were prepared by exposure of coupons of both alloys to lithiated aqueous solutions, under hydrothermal conditions and hydrogen overpressure, simulating PHWR conditions. Oxide layer morphology, the influence of exposure time to corrosive medium and LiOH concentration on its thickness were characterized. Descaling tests consisting on a two-stage method (a first oxidizing step with alkaline permanganate followed by a reducing step with oxalic or malonic acid were carried out). Results were compared to those obtained with a well known chemical cleaning formulation (APAC: Alkaline Permanganate Ammonium Citrate) used in decontamination of several reactors and loops and the competitiveness of malonic acid was demonstrated.

  5. 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

  6. 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.

  7. Phase diagrams and water activities of aqueous ammonium salts of malonic acid.

    PubMed

    Beyer, Keith D; Richardson, Michael; Reusch, Breanna

    2011-04-14

    Malonic acid has been observed in the free troposphere and as a component of tropospheric aerosol, among other dicarboxylic acids. These aerosols can uptake ammonia, which partially or completely neutralizes the acids. Therefore, the impact of ammoniated dicarboxylic acids on the phases that can exist in aerosols at atmospheric temperatures needs investigation. To that end, the low temperature, solid/liquid phase diagrams of ammonium hydrogen malonate/water, ammonium malonate/water, and triammonium hydrogen malonate/water have been investigated with differential scanning calorimetry and infrared spectroscopy of thin films. Results show that the order of increasing solubility is triammonium hydrogen malonate, ammonium hydrogen malonate, malonic acid, and ammonium malonate. We have also determined a hydrate may form in the ammonium malonate system and decompose below 240 K. We report water activities at the ice melting points for each system up to the respective eutectic concentrations, and find for a given mole fraction of water, increasing ammonium content leads to decreasing water activity coefficients. PMID:21428389

  8. 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.

  9. Ascorbic acid intake and oxalate synthesis.

    PubMed

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

    2016-08-01

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

  10. Vacuolar deposition of ascorbate-derived oxalic acid in barley

    SciTech Connect

    Wagner, G.J.

    1981-03-01

    L-(1-/sup 14/C)Ascorbic acid was supplied to detached barley seedlings to determine the subcellular location of oxalic acid, one of its metabolic products. Intact vacuoles isolated from protoplasts of labeled leaves contained (/sup 14/C)oxalic acid which accounted for about 70% of the intraprotoplast soluble oxalic acid. Tracer-labeled oxalate accounted for 36 and 72% of the /sup 14/C associated with leaf vacuoles of seedlings labeled for 22 and 96 hours, respectively.

  11. 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.

  12. The anodizing behavior of aluminum in malonic acid solution and morphology of the anodic films

    NASA Astrophysics Data System (ADS)

    Ren, Jianjun; Zuo, Yu

    2012-11-01

    The anodizing behavior of aluminum in malonic acid solution and morphology of the anodic films were studied. The voltage-time response for galvanostatic anodization of aluminum in malonic acid solution exhibits a conventional three-stage feature but the formation voltage is much higher. With the increase of electrolyte concentration, the electrolyte viscosity increases simultaneously and the high viscosity decreases the film growth rate. With the concentration increase of the malonic acid electrolyte, the critical current density that initiates local "burning" on the sample surface decreases. For malonic acid anodization, the field-assisted dissolution on the oxide surface is relatively weak and the nucleation of pores is more difficult, which results in greater barrier layer thickness and larger cell dimension. The embryo of the porous structure of anodic film has been created within the linear region of the first transient stage, and the definite porous structure has been established before the end of the first transient stage. The self-ordering behavior of the porous film is influenced by the electrolyte concentration, film thickness and the applied current density. Great current density not only improves the cell arrangement order but also brings about larger cell dimension.

  13. 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.

  14. Long-lived oscillations in the chlorite-iodide-malonic acid reaction in batch

    SciTech Connect

    Noszticzius, Z.; Ouyang, Qi; McCormick, W.D.; Swinney, H.L.

    1992-05-20

    The title reaction is the subject of current interest because the first experimental Turing patterns were observed recently in this system. Here, the authors report the first observation of oscillations that are long lived (over 1 h) in this system in a batch reactor; even after cessation the oscillations can be restarted several times by adding ClO{sub 2} to the exhausted system. These low-frequency low-amplitude (LL) oscillations were detected with both platinum and iodide-selective electrodes in the chlorite-iodide-malonic acid (original CIMA) reaction and in the closely related chlorine dioxide-iodide-malonic acid (minimal CIMA) system. The LL oscillations follow after the already known high frequency oscillations, sometimes separated by a second induction period. LL oscillations can appear without any induction period if appropriate concentrations of chlorine dioxide, iodomalonic acid, and chloride (CIMA-Cl system) are established in a dilute sulfuric acid medium. In this case neither iodine, iodide, nor malonic acid is needed. Some suggestions are made regarding the mechanism of these newly discovered oscillations. 33 refs., 6 figs., 1 tab.

  15. 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.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-08-01

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

  19. 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.

  20. Characterization of oxalic acid pretreatment on lignocellulosic biomass using oxalic acid recovered by electrodialysis.

    PubMed

    Lee, Hong-Joo; Seo, Young-Jun; Lee, Jae-Won

    2013-04-01

    The properties of pretreated biomass and hydrolysate obtained by oxalic acid pretreatment using oxalic acid recovered through electrodialysis (ED) were investigated. Most of the oxalic acid was recovered and some of the fermentation inhibitors were removed by ED. For the original hydrolysate, the ethanol production was very low and fermentable sugars were not completely consumed by Pichia stipitis during fermentation. Ethanol yield was less than 0.12 g/g in all stage. For the ED-treated hydrolysate, ethanol production was increased by up to two times in all stages compared to the original hydrolysate. The highest ethanol production was 19.38 g/l after 72 h which correspond to the ethanol yield of 0.33 g/g. Enzymatic conversion of the cellulose to glucose for all the pretreated biomass was in the range of 76.03 and 77.63%. The hydrolysis rate on each pretreated biomass was not significantly changed when oxalic acid recovered by ED was used for pretreatment. PMID:23422303

  1. 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.

  2. Lone-pair interactions in the photoelectron spectra of dicarboxylic acids: malonic acid and its α-alkyl derivatives

    NASA Astrophysics Data System (ADS)

    Ajò, D.; Ciliberto, E.; Fragalà, I.; Granozzi, G.

    1980-02-01

    Photoelectron spectra of malonic, methylmalonic and diethylmalonic acids are reported. The energy splitting of photoelectron bands representing carbonyl oxygen lone pairs is due to a "through-bond" interaction mechanism. The magnitude of the splitting depends upon the α-alkyl substitution because of conformational effects.

  3. Toxicity to embryo and adult zebrafish of copper complexes with two malonic acids as models for dissolved organic matter

    SciTech Connect

    Palmer, F.B.; Evans, C.W.; Butler, C.A.; Timperley, M.H.

    1998-08-01

    The toxicity to embryo and adult zebrafish (Danio rerio) of Cu complexes with two substituted malonic acids, benzyl- and n-hexadecyl-, chosen as models for low-molecular-weight natural dissolved organic matter, were investigated. Toxicity test solutions at pH 6.5 {+-} 0.1 with the required Cu ion-specific electrode. In the absence of malonic acids, concentrations of Cu{sup 2+} up to 1.13 {mu}mol/L increased the embryo hatching time from approx. 2 d in control solutions (no Cu or malonic acid) and solutions containing malonic acids without Cu to approx. 8 d. The Cu-benzylmalonic acid complex in the presence of inorganic Cu species did not delay hatching beyond that attributable to Cu{sup 2+}. In contrast, 0.60 {mu}mol/L Cu-n-hexadecylmalonic complexes delayed hatching by 5.5 d in excess of that attributable to 1.13 {mu}mol/L Cu{sup 2+}, assuming that the hatching delays caused by the different Cu species were additive, possibly because of Cu entry into the embryo as the lipophilic Cu-n-hexadecylmalonic complex. None of the Cu-malonic acid complexes was acutely toxic to adult zebrafish at concentrations up to 1.4 {mu}mol/L, possibly because Cu was removed from the Cu-malonic acid complexes by stronger chelating groups at the gill surface. Substituted malonic acids with similar proton and Cu association constants can be readily prepared with a variety of simple substituents, radiolabeled if required. Their results show that these acids could be useful ligands for investigating intracellular transport and metabolism of metal-organic complexes.

  4. 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

  5. Oxalic acid in saliva, teeth and tooth tartar.

    PubMed

    Wahl, R; Kallee, E

    1994-11-01

    Oxalic acid was determined in human saliva, teeth, tartar, and in animal teeth. Saliva from dentally healthy male subjects contained 0.10 +/- 0.09 mmol/l (n = 41) and those of dentally healthy female subjects 0.18 +/- 0.17 mmol/l (n = 40). Oxalic acid in tartar from 16 patients was 3.3 +/- 1.2 mmol/kg tartar. In human teeth, oxalic acid was 1.0 +/- 0.3 mmol/kg in milk teeth (n = 12) and 0.9 +/- 0.6 mmol/kg in permanent teeth (n = 60). Human teeth were sorted into age groups and into molars, incisors and premolars. In animal teeth, oxalic acid content varied widely. The formed calcium oxalate is proposed to be a 'physiological' protective mechanism for teeth. PMID:7888477

  6. 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.

  7. Malone refrigeration

    SciTech Connect

    Swift, G.W.

    1993-01-01

    Malone refrigeration is the use of a liquid near its critical points without evaporations as working fluid in a regenerative or recuperative refrigeration cycle such as the Stirling and Brayton cycles. It's potential advantages include compactness, efficiency, an environmentally benign working fluid, and reasonable cost. One Malone refrigerator has been built and studied; two more are under construction. Malone refrigeration is such a new, relatively unexplored technology that the potential for inventions leading to improvements in efficiency and simplicity is very high.

  8. 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

  9. 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

  10. Equilibrium phase diagrams and water absorption properties of aqueous mixtures of malonic acid and inorganic salts.

    NASA Astrophysics Data System (ADS)

    Salcedo, D.; Salgado-Olea, G.

    2006-12-01

    Tropospheric aerosols are usually complex mixtures of inorganic and organic components. Although the thermodynamic properties of inorganic aerosols have been widely studied, the effect of organics on such properties is still under discussion. Solubility in water, water activity of aqueous solutions, deliquescence relative humidity (DRH), eutonic composition, and eutonic DRH were determined for bulk mixtures of malonic acid with ammonium sulfate, ammonium bisulfate, and ammonium nitrate at 25oC over the full range of composition (from 0 wt% to the solubility limit of the mixture components). The data was used to construct equilibrium phase diagrams, which show the phase of the mixtures as a function of total composition, dry mixture composition, water content, and ambient relative humidity. Measured water activity of liquid solutions was compared with an extended Zdanovskii-Stokes-Robinson (ZSR) expression, which then was used to predict water absorption of the mixtures.

  11. Malone refrigeration

    SciTech Connect

    Swift, G.W.

    1993-06-01

    Malone refrigeration is the use of a liquid near its critical points without evaporations as working fluid in a regenerative or recuperative refrigeration cycle such as the Stirling and Brayton cycles. It`s potential advantages include compactness, efficiency, an environmentally benign working fluid, and reasonable cost. One Malone refrigerator has been built and studied; two more are under construction. Malone refrigeration is such a new, relatively unexplored technology that the potential for inventions leading to improvements in efficiency and simplicity is very high.

  12. Poly(2-thiophen-3-yl-malonic acid), a polythiophene with two carboxylic acids per repeating unit.

    PubMed

    Bertran, Oscar; Armelin, Elaine; Estrany, Francesc; Gomes, Alex; Torras, Juan; Alemán, Carlos

    2010-05-20

    A new substituted polythiophene derivative bearing malonic acid, poly(2-thiophen-3-yl-malonic acid), has been prepared and characterized using a strategy that combines both experimental and theoretical methodologies. The chemical structure of this material has been investigated using FTIR and (1)H NMR, and its molecular conformation has been determined using quantum mechanical calculations. Interestingly, the arrangement of the inter-ring dihedral angles was found to depend on the ionization degree of the material, that is, on the pH, which has been found completely soluble in aqueous base solution. Thus, the preferred anti-gauche conformation changes to syn-gauche when the negatively charged carboxylate groups transforms into neutral carboxylic acid. UV-vis experiments and quantum mechanical calculations on model systems with a head-to-tail regiochemistry showed that the lowest pi-pi* transition energy is 2.25 and 2.39 eV for the negatively charged and the neutral polymer, respectively. These values are slightly larger than those previously reported for other polythiophenes with bulky polar side groups. The polymer presents a good thermal stability with a decomposition temperature above 215 degrees C and an electrical conductivity of 10(-5) S/cm, which is characteristic of semiconductor materials. Scanning electron microscopy micrographs showed that, after doping, the surface of this material displays regular distribution pores with irregular sizes. This surface suggests that poly(2-thiophen-3-yl-malonic acid) is a candidate for potential applications such as selective membranes for electrodialysis, wastewater treatment, or ion-selective membranes for biomedical uses. PMID:20411968

  13. A biogenic source of oxalic acid in marine aerosol

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

    Oxalic acid has been often observed in marine aerosol, nevertheless, given the ubiquitous character and the high concentrations found in polluted environments, its origin has often been attributed to continental sources. In this work, we present the results of oxalic acid analyses, on aerosol samples collected 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. Measurements cover the year 2006, at the Northern Hemisphere site, and the period 2003-2007, at the Southern Hemisphere one. 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

  14. Malone refrigeration

    SciTech Connect

    Swift, G W

    1992-01-01

    Malone refrigeration is the use of a liquid near its critical point, without evaporation, as working fluid in a refrigeration cycle such as the Stirling cycle. We discuss relevant properties of appropriate liquids, and describe two Malone refrigerators. The first completed several years ago, established the basic principles of use of liquids in such cycles. The second, now under construction, is a linear, free-piston machine.

  15. 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.

  16. 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

  17. Acute renal failure following oxalic acid poisoning: a case report

    PubMed Central

    2012-01-01

    Oxalic acid poisoning is being recognized as an emerging epidemic in the rural communities of Sri Lanka as it is a component of locally produced household laundry detergents. Herein we describe a case of a 32 year old female, presenting after direct ingestion of oxalic acid. She then went on to develop significant metabolic acidosis and acute renal failure, requiring dialysis. Renal biopsy revealed acute tubulointerstitial nephritis associated with diffuse moderate acute tubular damage with refractile crystals in some of the tubules. The patient symptomatically improved with haemodialysis and renal functions subsequently returned to normal. PMID:22978510

  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. 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

  20. 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}.

  1. 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.

  2. 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

  3. 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

  4. Equilibrium phase diagrams of aqueous mixtures of malonic acid and sulfate/ammonium salts.

    PubMed

    Salcedo, Dara

    2006-11-01

    Tropospheric aerosols are usually complex mixtures of inorganic and organic components. Although the thermodynamic properties of inorganic aerosols have been widely studied, the effect of organics on such properties is still under discussion. In this study, solubility in water, water activity (a(w)) of aqueous solutions, deliquescence relative humidity (DRH), eutonic composition, and eutonic DRH were determined for bulk mixtures of malonic acid (MA) with ammonium sulfate (AS) and ammonium bisulfate (ABS) at 25 degrees C over the full range of composition (from 0 wt % to the solubility limit of the mixture components). The data were used to construct equilibrium phase diagrams, which show the phase of the mixtures as a function of total composition, dry mixture composition, water content, and ambient relative humidity (RH). This work complements previous reports on the thermodynamic properties of AS/MA mixtures because the range of concentrations investigated is larger than in any other published single study. On the other hand, this is the first report on the a(w), deliquescence, and water absorption of ABS/MA mixtures. The eutonic composition for AS/MA mixtures was found to be 66.8 MA dry wt % (MA dry wt % = MA mass x 100/(AS mass + MA mass) with a DRH of 0.437. The eutonic composition for the ABS/MA mixtures was lower than for the AS/MA mixtures: 20.9 MA dry wt % with a DRH of 0.327. Measured a(w) of liquid AS/MA and ABS/MA solutions is compared with an extended Zdanovskii-Stokes-Robinson expression, obtaining a good agreement (error < 5-6%). The expression was used to predict water uptake of mixtures and might be useful to interpret particle hygroscopic growth experiments. Comparison of the AS/MA and ABS/MA systems indicates that ABS reduces the DRH and enhances water uptake, relative to mixtures with AS. The results confirm that ambient particles containing sulfate and water-soluble organic compounds can remain liquid or partially liquid at very low ambient RH

  5. Structures of malonic acid diamide/phospholipid composites and their lipoplexes.

    PubMed

    Janich, Christopher; Taßler, Stephanie; Meister, Annette; Hause, Gerd; Schäfer, Jens; Bakowsky, Udo; Brezesinski, Gerald; Wölk, Christian

    2016-07-01

    As a continuation of previous work, the self-assembly process of cationic lipid formulations in the presence and absence of DNA was investigated with respect to binary lipid mixtures suitable as polynucleotide carrier systems. The lipid blends consist of one malonic-acid-based cationic lipid with a varying alkyl chain pattern, either N-{6-amino-1-[N-(9Z)-octadec-9-enylamino]-1-oxohexan-(2S)-2-yl}-N'-{2-[N,N-bis(2-aminoethyl)amino]ethyl}-2-hexadecylpropandiamide () or N-[6-amino-1-oxo-1-(N-tetradecylamino)hexan-(2S)-2-yl]-N'-{2-[N,N-bis(2-aminoethyl)amino]ethyl}-2-hexadecylpropandiamide (), and one neutral co-lipid, either 1,2-di-[(9Z)-octadec-9-enoyl]-sn-glycero-3-phosphocholine (DOPE) or 1,2-di-(hexadecanoyl)-sn-glycero-3-phosphocholine (DPPC). Although the cationic lipids exhibit only slight differences in their structure, the DNA transfer efficiency varies drastically. Therefore, self-assembly was studied in 3D systems by small- and wide-angle X-ray scattering (SAXS and WAXS) and transmission electron microscopy (TEM) as well as in 2D systems by infrared reflection-absorption spectroscopy (IRRAS) on Langmuir films. The investigated lipid mixtures show quite different self-assembly in the absence of DNA, with varying structures from vesicles (/DOPE; /DOPE) and tubes (/DOPE) to discoid structures (/DPPC; /DPPC). Twisted ribbons and sheets, which were stabilized due to hydrogen-bond networks, were found in all investigated lipid mixtures in the absence of DNA. The addition of DNA leads to the formation of lamellar lipoplexes for all the investigated lipid compositions. The lipoplexes differ in crucial parameters, such as the lamellar repeat distance and the spacing between the DNA strands, indicating differences in the binding strength between DNA and the lipid composition. The formation of associates with an ideal charge density might emerge as a key parameter for efficient DNA transfer. Furthermore, the structures observed for the different lipid compositions in

  6. 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

  7. 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.

  8. 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 ...

  9. Studies on the adsorption of americium on alumina from aqueous nitric acid-oxalic acid solutions

    SciTech Connect

    Subba Rao, M.; Gaikwad, A.M.; Rao, V.K.; Natarajan, P.R.

    1985-01-01

    This paper reports a study on the adsorption of Am(III) on alumina from oxalic acid-nitric acid solutions. Distribution coefficients for Am(III) on alumina at different oxalic acid-nitric acid concentrations have been determined and optimum conditions for loading and elution of Am from alumina columns have been established. Separation of Am from Pu and the effects of other ions, such as U(VI) and Fe(III), have also been studied. Am and Pu recoveries better than 99.5% were obtained. 3 references, 2 figures, 5 tables.

  10. 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

  11. Hydroxyl radical substitution in halogenated carbonyls: oxalic acid formation.

    PubMed

    Christiansen, Carrie J; Dalal, Shakeel S; Francisco, Joseph S; Mebel, Alexander M; Gaffney, Jeffrey S

    2010-03-01

    An ab initio study of OH radical substitution reactions in halogenated carbonyls is conducted. Hydroxyl radical substitution into oxalyl dichloride [ClC(O)C(O)Cl] and oxalyl dibromide [BrC(O)C(O)Br], resulting in the formation of oxalic acid, is presented. Analogous substitution reactions in formyl chloride [ClCH(O)], acetyl chloride [ClC(O)CH(3)], formyl bromide [BrCH(O)], and acetyl bromide [BrC(O)CH(3)] are considered. Energetics of competing hydrogen abstraction reactions for all applicable species are computed for comparison. Geometry optimizations and frequency computations are performed using the second-order Møller-Plesset perturbation theory (MP2) and the 6-31G(d) basis set for all minimum species and transition states. Single point energy computations are performed using fourth-order Møller-Plesset perturbation theory (MP4) and coupled cluster theory [CCSD(T)]. Potential energy surfaces, including activation energies and enthalpies, are determined from the computations. These potential energy surfaces show that OH substitution into ClC(O)C(O)Cl and BrC(O)C(O)Br, resulting in the formation of oxalic acid and other minor products, is energetically favorable. Energetics of analogous reactions with ClCH(O), BrCH(O), ClC(O)CH(3), and BrC(O)CH(3) are also computed. PMID:20131850

  12. Pseudomonas fluorescens ATCC 13525 containing an artificial oxalate operon and Vitreoscilla hemoglobin secretes oxalic acid and solubilizes rock phosphate in acidic alfisols.

    PubMed

    Yadav, Kavita; Kumar, Chanchal; 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

  13. Catalytic kinetic spectrophotometry for the determination of trace amount of oxalic acid in biological samples with oxalic acid-rhodamine B-potassium dichromate system

    NASA Astrophysics Data System (ADS)

    Zhai, Qing-Zhou; Zhang, Xiao-Xia; Liu, Qing-Zhou

    2006-09-01

    A new catalytic kinetic spectrophotometric method was proposed for determining trace oxalic acid based on the catalytic effect of oxalate on the oxidation of potassium dichromate with rhodamin B in 0.10 M of sulfuric acid. Good linearity is obtained over the concentration range 0.40-6.0 μg/mL of oxalic acid. After the reactions of the catalytic and non-catalytic systems were terminated by using 2.00 mL of 4 M sodium hydroxide solution, they can be stable for 3 h at room temperature. The apparent activation energy of the catalytic reaction is 12.44 kJ/mol. The effect of 50 coexisting substances was observed. The method was used to determine trace oxalic acid in tea, spinach and urine samples with satisfactory results.

  14. The fluorimetric determination of oxalic acid in blood and other biological materials

    PubMed Central

    Zarembski, P. M.; Hodgkinson, A.

    1965-01-01

    1. Oxalic acid is separated from interfering substances by extraction with tri-n-butyl phosphate followed by co-precipitation with calcium sulphate. The precipitated oxalic acid is then reduced to glyoxylic acid, which is coupled with resorcinol to form a coloured fluorescent complex. 2. The spectrofluorometric method described is sensitive and highly specific, the minimum detectable amount of oxalic acid being 0·9μmole under the recommended conditions. 3. The concentration of oxalic acid in blood from 15 normal adults was 200–320μg./100ml. For serum the range was 135–280μg./100ml. The urinary excretion of oxalic acid by 60 normal adults on a normal diet was 9·0–28·5mg./24hr. PMID:5862411

  15. Organocatalytic enantioselective decarboxylative reaction of malonic acid half thioesters with cyclic N-sulfonyl ketimines by using N-heteroarenesulfonyl cinchona alkaloid amides.

    PubMed

    Nakamura, Shuichi; Sano, Masahide; Toda, Ayaka; Nakane, Daisuke; Masuda, Hideki

    2015-03-01

    The organocatalytic enantioselective decarboxylative Mannich reaction of malonic acid half thioesters (MAHTs) with cyclic N-sulfonyl ketimines by using N-heteroarenesulfonyl cinchona alkaloid amides afforded products with high enantioselectivity. Both enantiomers of the products could be obtained by using pseudoenantiomeric chiral catalysts. The reaction proceeds through a nucleophilic addition of the MAHTs to the ketimines prior to decarboxylation. PMID:25614368

  16. 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. PMID:26970042

  17. 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...

  18. Comparison of oxalate formation from ascorbic and glyoxyl acids in detached glandular heads of tobacco trichomes

    SciTech Connect

    Vogeli-Lange, R.; Wagner, G.J.

    1987-08-01

    Ca-oxalate crystal containing cells from detached glandular heads of trichomes from Nicotiana tabacum, TI 1068, are capable of converting (1-/sup 14/C) ascorbic acid (AA) and (1-/sup 14/C) glyoxylic acid (GA) to oxalate. AA was found to be a better precursor for oxalate formation than GA. In detached glandular heads, 3.6x more label was converted to oxalate from AA than from GA, in the epidermis the factor was 3x while that with petiole tissue was 7x. Oxalate formation from AA, in detached glandular heads, was only partially inhibited in the dark and in the presence of metabolic inhibitors, suggesting that a nonenzymatic component might be involved. Oxalate formation from GA increased in the presence of metabolic inhibitors. During treatment of detached glandular heads with 2 mM Ca-acetate for 2 days, oxalate formation from AA was stimulated 3 fold, while the presence of 2mM Ca-acetate had no effect on the oxalate formation from GA. These results suggest that Ca/sup 2 +/ stimulates the formation of Ca-oxalate crystals in glandular head cells, and that AA can serve as a precursor for oxalate production.

  19. 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.

  20. 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.

  1. 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.

  2. Modeling aqueous ozone/UV process using oxalic acid as probe chemical.

    PubMed

    Garoma, Temesgen; Gurol, Mirat D

    2005-10-15

    A kinetic model that describes the removal of organic pollutants by an ozone/UV process is described. Oxalic acid, which reacts with a very low rate constant with ozone and relatively high rate constant with hydroxyl radical (OH*), was used as the probe chemical to model the process. The model was verified by experimental data on concentrations of oxalic acid and hydrogen peroxide (H202) under various experimental conditions, i.e., ozone gas dosage, UV light intensity, and varying oxalic acid concentrations. PMID:16295862

  3. 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

  4. 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

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

    NASA Astrophysics Data System (ADS)

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

    2008-09-01

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

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. Oxalic acid capped iron oxide nanorods as a sensing platform.

    PubMed

    Sharma, Anshu; Baral, Dinesh; Bohidar, H B; Solanki, Pratima R

    2015-08-01

    A label free impedimetric immunosensor has been fabricated using protein bovine serum albumin (BSA) and monoclonal antibodies against Vibrio cholerae (Ab) functionalized oxalic acid (OA) capped iron oxide (Fe3O4) nanorods for V. cholerae detection. The structural and morphological studies of Fe3O4 and OA-Fe3O4, were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and dynamic light scattering (DLS) techniques. The average crystalline size of Fe3O4, OA-Fe3O4 nanorods were obtained as about 29±1 and 39±1nm, respectively. The hydrodynamic radius of nanorods is found as 116nm (OA-Fe3O4) and 77nm (Fe3O4) by DLS measurement. Cytotoxicity of Fe3O4 and OA-Fe3O4 nanorods has been investigated in the presence of human epithelial kidney (HEK) cell line 293 using MTT assay. The cell viability and proliferation studies reveal that the OA-Fe3O4 nanorods facilitate cell growth. The results of electrochemical response studies of the fabricated BSA/Ab/OA-Fe2O3/ITO immunosensor exhibits good linearity in the range of 12.5-500ng mL(-1) with low detection limit of 0.5ng mL(-1), sensitivity 0.1Ωng(-1)ml(-1)cm(-2) and reproducibility more than 11 times. PMID:26048074

  11. Oxalic acid: a signal molecule for fungus-feeding bacteria of the genus Collimonas?

    PubMed

    Rudnick, M B; van Veen, J A; de Boer, W

    2015-10-01

    Mycophagous (=fungus feeding) soil bacteria of the genus Collimonas have been shown to colonize and grow on hyphae of different fungal hosts as the only source of energy and carbon. The ability to exploit fungal nutrient resources might require a strategy for collimonads to sense fungi in the soil matrix. Oxalic acid is ubiquitously secreted by soil fungi, serving different purposes. In this study, we investigated the possibility that collimonads might use oxalic acid secretion to localize a fungal host and move towards it. We first confirmed earlier indications that collimonads have a very limited ability to use oxalic acid as growth substrate. In a second step, with using different assays, we show that oxalic acid triggers bacterial movement in such a way that accumulation of cells can be expected at micro-sites with high free oxalic acid concentrations. Based on these observations we propose that oxalic acid functions as a signal molecule to guide collimonads to hyphal tips, the mycelial zones that are most sensitive for mycophagous bacterial attack. PMID:25858310

  12. 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.

  13. 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...

  14. Dissolution of nickel ferrite in aqueous solutions containing oxalic acid and ferrous salts

    SciTech Connect

    Figueroa, C.A.; Sileo, E.E.; Morando, P.J.; Blesa, M.A.

    2000-05-15

    The dissolution of nickel ferrite in oxalic acid and in ferrous oxalate-oxalic acid aqueous solution was studied. Nickel ferrite was synthesized by thermal decomposition of a mixed tartrate; the particles were shown to be coated with a thin ferric oxide layer. Dissolution takes place in two stages, the first one corresponding to the dissolution of the ferric oxide outer layer and the second one being the dissolution of Ni{sub 1.06}Fe{sub 1.96}O{sub 4}. The kinetics of dissolution during this first stage is typical of ferric oxides: in oxalic acid, both a ligand-assisted and a redox mechanism operates, whereas in the presence of ferrous ions, redox catalysis leads to a faster dissolution. The rate dependence on both oxalic acid and on ferrous ion is described by the Langmuir-Hinshelwood equation. In the second stage, Langmuir-Hinshelwood kinetics also describes the dissolution of iron and nickel from nickel ferrite. It may be concluded that oxalic acid operates to dissolve iron, and the ensuing disruption of the solid framework accelerates the release of nickel.

  15. New cloud chamber experiments on the heterogeneous ice nucleation ability of oxalic acid in the deposition nucleation and immersion freezing modes

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

    Dicarboxylic acids are ubiquitous components of the water-soluble organic fraction of the tropospheric aerosol. Their contribution to the total particulate organic carbon typically ranges from 1 - 3 wt% in urban and semi-urban areas to up to 10 wt% in remote marine atmospheres [1,2]. Oxalic acid, malonic acid, and succinic acid are usually the most abundant species, partly comprising more than 80% of the total diacid mass concentrations [3]. Several recent studies have addressed the ice nucleation potential of solid low-molecular weight dicarboxylic acids. On the one hand, the dicarboxylic acids can act as deposition mode ice nuclei provided that they are directly exposed to an ice supersaturated environment, e.g. in form of a coating layer that was formed by physical and chemical processing on prevalent particulates such as mineral dust and soot. At typical tropospheric relative humidities, diacids of low water solubility like oxalic and succinic acid may, on the other hand, also be present as solids that are immersed in aqueous inorganic and/or organic solution droplets [4,5]. These embedded crystals can act as ice nuclei in the immersion mode. Here we present new results from recent experiments at the aerosol and cloud chamber facility of the Karlsruhe Institute of Technology. The ice nucleation ability of aqueous and crystalline oxalic acid aerosol particles was investigated at expansion cooling conditions in the temperature range between 244 and 228 K [6]. Oxalic acid dihydrate particles with diameters between 0.03 to 0.8 μm, that were either formed by nucleation from a gaseous oxalic acid/air mixture or by rapid crystallisation of highly supersaturated aqueous oxalic acid solution droplets, showed a high deposition mode ice activity at temperatures around 244 K. The ice onset humidity was below 110 % with respect to ice, and the ice-active fraction of the aerosol population was in the range from 0.1 to 22%. In contrast, oxalic acid dihydrate particles

  16. 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

  17. 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

  18. 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

  19. 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.

  20. 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. PMID:26851896

  1. 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.

  2. Equilibrium aluminium hydroxo-oxalate phases during initial clay formation; H +-Al 3+-oxalic acid-Na + system

    NASA Astrophysics Data System (ADS)

    Bilinski, Halka; Horvath, Laszlo; Ingri, Nils; Sjöberg, Staffan

    1986-09-01

    The conditions necessary for initial clay formation have been studied in different model systems comprising different organic acids besides Si and Al. In the present paper the solid phases and the precipitation boundary characterizing the subsystem H +-Al 3+-oxalic acid (H 2L) are discussed. pH and tyndallometric measurements were performed in an ionic medium of 0.6 M Na(Cl) at 25 °C. The two phases Al 3(OH) 7(C 2O 4) · 3H 2O (phase I) and NaAl(OH) 2(C 2O 4) · 3H 2O (phase II) determine the precipitation boundary. The following formation constants for the two phases were deduced: lgβ1 = lg([ Al3+] -3[ H2C2O4] -1[ H+] 9 = -21.87 ± 0.08 and lgβ11 = lg([ Al3+] -1[ H2C2O4] -1[ H+] 4 = -5.61 ± 0.06. Phase I exists in the range [ Al] tot≥ 10 -4.4moldm-3,[ H2C2O4] tot ≥ 10 -4.9moldm-3 and at pH < 6.8, thus being a possible precipitate in oxalic-rich natural waters. The more soluble sodium phase is unlikely to exist in natural waters. The two phases are metastable relative to crystalline gibbsite and may be considered as the first precipitation step in the transition from aqueous Al oxalates down to stable Al hydroxide. Model calculations illustrating these competing hydrolysis-complexation reactions are discussed in terms of predominance and speciation diagrams. The solid phases have been characterized by X-ray analysis of powders, TGA and IR spectra, and tentative structures are proposed. Phase I seems to be an octahedral layer structure, in which 3/5 of the octahedral sites between two close packed oxygen sheets are occupied by Al 3+ and the oxalate ion acts as a bridge ligand between two aluminium atoms. Phase II forms a more open sheet structure and has ion exchange properties. Powder data for a phase crystallized from the studied solution after a year are also presented. This phase, Na 4Al 2(OH) 2(C 2O 4) 4 · 10H 2O, supports the results from the equilibrium analysis of recent solution data by SJöBERG and ÖHMAN (1985), who have found the dinuclear

  3. Influence of Amitraz and Oxalic Acid on the Cuticle Proteolytic System of Apis mellifera L. Workers

    PubMed Central

    Strachecka, Aneta; Paleolog, Jerzy; Olszewski, Krzysztof; Borsuk, Grzegorz

    2012-01-01

    This work verifies that amitraz and oxalic acid treatment affect honeybee cuticle proteolytic enzymes (CPE). Three bee groups were monitored: oxalic acid treatment, amitraz treatment, control. Electrophoresis of hydrophilic and hydrophobic CPE was performed. Protease and protease inhibitor activities (in vitro) and antifungal/antibacterial efficiencies (in vivo), were analyzed. Amitraz and oxalic acid treatment reduced hydrophobic, but did not affect hydrophilic, protein concentrations and reduced both hydrophilic and hydrophobic body surface asparagine and serine protease activities in relation to most substrates and independently of pH. The activities of natural cuticle inhibitors of acidic, neutral, and alkaline proteases were suppressed as a result of the treatments, corresponding with reduced antifungal and antibacterial activity. Electrophoretic patterns of low-, medium-, and high-molecular-weight proteases and protease inhibitors were also affected by the treatments. PMID:26466630

  4. 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

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

    NASA Astrophysics Data System (ADS)

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

    2011-08-01

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

  6. Ion exhange and molecular sorption of oxalic acid with a highly basic anion exchanger

    NASA Astrophysics Data System (ADS)

    Krisilova, E. V.; Oros, G. Yu.; Krisilov, A. V.; Selemenev, V. F.

    2014-04-01

    Ab initio modeling of a matrix fragment of resin and geometry optimization of the molecular structure of oxalic acid were performed. The isotherm of oxalic acid sorption with AV-17-8 anion exchange resin was obtained by the variable concentrations technique. The ion-exchange and molecular components of sorbate fixation with the ion exchanger were determined. The hydration of the highly basic anion exchanger that absorbed different quantities of dicarboxylic acid was evaluated by the centrifuging method. The dependence of the amount of water and sorbate concentration in the resin was linear antibatic.

  7. 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

  8. Oxalic acid alleviates chilling injury in peach fruit by regulating energy metabolism and fatty acid contents.

    PubMed

    Jin, Peng; Zhu, Hong; Wang, Lei; Shan, Timin; Zheng, Yonghua

    2014-10-15

    The effects of postharvest oxalic acid (OA) treatment on chilling injury, energy metabolism and membrane fatty acid content in 'Baifeng' peach fruit stored at 0°C were investigated. Internal browning was significantly reduced by OA treatment in peaches. OA treatment markedly inhibited the increase of ion leakage and the accumulation of malondialdehyde. Meanwhile, OA significantly increased the contents of adenosine triphosphate and energy charge in peach fruit. Enzyme activities of energy metabolism including H(+)-adenosine triphosphatase, Ca(2+)-adenosine triphosphatase, succinic dehydrogenase and cytochrome C oxidase were markedly enhanced by OA treatment. The ratio of unsaturated/saturated fatty acid in OA-treated fruit was significantly higher than that in control fruit. These results suggest that the alleviation in chilling injury by OA may be due to enhanced enzyme activities related to energy metabolism and higher levels of energy status and unsaturated/saturated fatty acid ratio. PMID:24837925

  9. 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

  10. 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

  11. 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...

  12. 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

  13. Hydrogen Generation During the Corrosion of Carbon Steel in Oxalic Acid

    SciTech Connect

    WIERSMA, BRUCEJ.

    2004-08-01

    A literature review of the corrosion mechanism for carbon steel in oxalic acid was performed to determine the ratio of moles of iron corroded to moles of hydrogen evolved during the corrosion of iron in oxalic acid. The theory of corrosion of carbon steel in oxalic acid and experimental work were reviewed. It was concluded that the maximum ratio of moles of hydrogen evolved to moles of iron corroded is 1:1. This ratio would be observed in a de-aerated environment. If oxygen or other oxidizing species are present, the ratio could be much less than 1:1. Testing would be necessary to determine how much less than 1:1 the ratio might be. Although the ratio of hydrogen evolution to iron corroded will not exceed 1:1, the total amount of hydrogen evolved can be influenced by such things as a decrease in the exposed surface area, suppression of hydrogen generation by gamma radiation, the presence of corrosion products on steel surface, etc. These and other variables present during chemical cleaning operations of the waste tank have not been examined by the tests reported in the literature i.e., the tests have focused on clean corrosion coupons in oxalic acid solutions. It is expected that most of these variables would reduce the total amount of hydrogen evolved. Further testing would need to be performed to quantify the reduction in hydrogen generation rate associated with these variables.

  14. 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

  15. 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. PMID:25178492

  16. 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. PMID:25662240

  17. 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.

  18. Malone cycle refrigerator development

    SciTech Connect

    Shimko, M.A.; Crowley, C.J.

    1999-07-01

    This paper describes the progress made in demonstrating a Malone Cycle Refrigerator/Freezer. The Malone cycle is similar to the Stirling cycle but uses a supercritical fluid in place of real gas. In the approach, solid-metal diaphragms are used to seal and sweep the working volumes against the high working fluid pressures required in Malone cycle machines. This feature eliminates the friction and leakage that accounted for nearly half the losses in the best piston-defined Malone cycle machines built to date. The authors successfully built a Malone cycle refrigerator that: (1) used CO{sub 2} as the working fluid, (2) operated at pressures up to 19.3 Mpa (2,800 psi), (3) achieved a cold end metal temperatures of {minus}29 C ({minus}20 F), and (4) produced over 400 Watts of cooling at near ambient temperatures. The critical diaphragm components operated flawlessly throughout characterization and performance testing, supporting the conclusion of high reliability based on analysis of fatigue date and actual strain measurements.

  19. 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

  20. Reactivation of an aged commercial three-way catalyst by oxalic and citric acid washing.

    PubMed

    Christou, Stavroula Y; Birgersson, Henrik; Fierro, José L G; Efstathiou, Angelos M

    2006-03-15

    The efficiency of dilute oxalic and citric acid solutions on improving the oxygen storage capacity (OSC) and catalytic activity of a severely aged (83,000 km) commercial three-way catalyst (TWC) has been investigated. Washing procedures applied after optimization of experimental parameters, namely, temperature, flow-rate, and concentration of acid solution, led to significant improvements of OSC and catalytic activity (based on dynamometer test measurements) of the aged TWC. The latterwas made possible due to the removal of significant amounts of various contaminants accumulated on the catalyst surface (e.g., P, S, Pb, Ca, Zn, Si, Fe, Cu, and Ni) during driving conditions, as revealed by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) and X-ray Photoelectron Spectroscopy (XPS) analyses. For the first time, it is demonstrated that dilute oxalic acid solution significantly improves the catalytic activity of an aged commercial TWC toward CO, Cx,Hy, and NOx conversions under real exhaust gas conditions (dynamometer tests) by two to eight times in the 250-450 degrees C range and the OSC quantity by up to 50%. Oxalic acid appears to be more efficient than citric acid in removing specifically P- and S-containing compounds from the catalyst surface, whereas citric acid in removing Pb- and Zn-containing compounds, thus uncovering surface active catalytic sites. PMID:16570632

  1. Proton transfer aiding phase transitions in oxalic acid dihydrate under pressure.

    PubMed

    Bhatt, Himal; Mishra, A K; Murli, Chitra; Verma, Ashok K; Garg, Nandini; Deo, M N; Sharma, Surinder M

    2016-03-21

    Oxalic acid dihydrate, an important molecular solid in crystal chemistry, ecology and physiology, has been studied for nearly 100 years now. The most debated issues regarding its proton dynamics have arisen due to an unusually short hydrogen bond between the acid and water molecules. Using combined in situ spectroscopic studies and first-principles simulations at high pressures, we show that the structural modification associated with this hydrogen bond is much more significant than ever assumed. Initially, under pressure, proton migration takes place along this strong hydrogen bond at a very low pressure of 2 GPa. This results in the protonation of water with systematic formation of dianionic oxalate and hydronium ion motifs, thus reversing the hydrogen bond hierarchy in the high pressure phase II. The resulting hydrogen bond between a hydronium ion and a carboxylic group shows remarkable strengthening under pressure, even in the pure ionic phase III. The loss of cooperativity of hydrogen bonds leads to another phase transition at ∼ 9 GPa through reorientation of other hydrogen bonds. The high pressure phase IV is stabilized by a strong hydrogen bond between the dominant CO2 and H2O groups of oxalate and hydronium ions, respectively. These findings suggest that oxalate systems may provide useful insights into proton transfer reactions and assembly of simple molecules under extreme conditions. PMID:26924455

  2. An ATP and oxalate generating variant tricarboxylic acid cycle counters aluminum toxicity in Pseudomonas fluorescens.

    PubMed

    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 CO(2)-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 O(2)-limited conditions. PMID:19809498

  3. Enhanced bioethanol production from yellow poplar by deacetylation and oxalic acid pretreatment without detoxification.

    PubMed

    Kundu, Chandan; Lee, Hong-Joo; Lee, Jae-Won

    2015-02-01

    In order to produce ethanol from yellow poplar, deacetylation was performed using sodium hydroxide (NaOH). Optimal deacetylation conditions were determined by a response surface methodology. The highest acetic acid concentration obtained was 7.06 g/L when deacetylation was performed at 60 °C for 80 min with 0.8% NaOH. Acetic acid was recovered by electrodialysis from the deacetylated hydrolysate. The oxalic acid pretreatment of deacetylated biomass was carried out and the hydrolysate directly used for ethanol production without detoxification. Ethanol yields ranged from 0.34 to 0.47 g/g and the highest ethanol yield was obtained when pretreatment was carried out at 150 °C with 50 mM oxalic acid. The highest ethanol concentration obtained from pretreated biomass was 27.21 g/L at 170 °C, using a 50 mM of oxalic acid for the simultaneous saccharification and fermentation (SSF). Overall, 20.31 g of ethanol was obtained by hydrolysate and SSF from 100 g of deacetylated yellow poplar. PMID:25205056

  4. 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…

  5. Production of oxalic acid from sugar beet molasses by formed nitrogen oxides.

    PubMed

    Gürü, M; Bilgesü, A Y; Pamuk, V

    2001-03-01

    Production of oxalic acid from sugar beet molasses was developed in a series of three reactors. Nitrogen oxides formed were used to manufacture oxalic acid in the second and third reactor. Parameters affecting the reaction were determined to be, air flow rate, temperature, the amount of V2O5 catalyst and the concentrations of molasses and H2SO4. The maximum yields in the second and third reactors were 78.9% and 74.6% of theoretical yield, respectively. Also, kinetic experiments were performed and the first-order rate constants were determined for the glucose consumption rate. Nitrogen oxides in off-gases from the final reactor were absorbed in water and concentrated sulphuric acid and reused in the following reactors giving slightly lower yields under similar conditions. In this novel way, it was possible to recover NO(x) and to prevent air pollution. Meanwhile, it was possible to reduce the unit cost of reactant for oxalic acid production. A maximum 77.5% and 74.1% of theoretical yield was obtained by using the absorption solutions with NO(x). PMID:11211079

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Bioethanol production from deacetylated yellow poplar pretreated with oxalic acid recovered through electrodialysis.

    PubMed

    Kundu, Chandan; Jeong, So-Yeon; Lee, Jae-Won

    2016-05-01

    Electrodialysis (ED) was used to develop a multistage oxalic acid recovery and pretreatment system to produce ethanol from deacetylated yellow poplar. Pretreatment of the biomass was performed at 150°C for 42 min using 0.16 M oxalic acid. The efficiency of oxalic acid recovery from the hydrolysate reached up to 92.32% in all the stages. Ethanol production and ethanol yield of ED-treated hydrolysate in each stage showed a uniform pattern ranging from 6.81 g/L to 7.21 g/L and 0.40 g/g to 0.43 g/g, respectively. The results showed that efficiency of ethanol production increased when deacetylated biomass and ED process was used. Ethanol yield from the pretreated biomass using simultaneous saccharification and fermentation (SSF) was in the range of 80.59-83.36% in all the stages. The structural characterization of the pretreated biomass at each stage was investigated and structural changes were not significantly different among the various pretreated biomass. PMID:26943934

  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. 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

  13. The effects of organic acids on the dissolution of silicate minerals: A case study of oxalate catalysis of kaolinite dissolution

    NASA Astrophysics Data System (ADS)

    Cama, Jordi; Ganor, Jiwchar

    2006-05-01

    Most studies agree that the dissolution rate of aluminosilicates in the presence of oxalic and other simple carboxylic acids is faster than the rate with non-organic acid under the same pH. However, the mechanisms by which organic ligands enhance the dissolution of minerals are in debate. The main goal of this paper was to study the mechanism that controls the dissolution rate of kaolinite in the presence of oxalate under far from equilibrium conditions (-29 < Δ Gr < -18 kcal mol -1). Two types of experiments were performed: non-stirred flow-through dissolution experiments and batch type adsorption isotherms. All the experiments were conducted at pH 2.5-3.5 in a thermostatic water-bath held at a constant temperature of 25.0, 50.0 or 70.0 ± 0.1 °C. Kaolinite dissolution rates were obtained based on the release of silicon and aluminum at steady state. The results show good agreement between these two estimates of kaolinite dissolution rate. At constant temperature, there is a general trend of increase in the overall dissolution rate as a function of the total concentration of oxalate in solution. The overall kaolinite dissolution rates in the presence of oxalate was up to 30 times faster than the dissolution rate of kaolinite at the same temperature and pH without oxalate as was observed in our previous study. Therefore, these rate differences are related to differences in oxalate and aluminum concentrations. Within the experimental variability, the oxalate adsorption at 25, 50, and 70 °C showed the same dependence on the sum of the activities of oxalate and bioxalate in solution. The change of oxalate concentration on the kaolinite surface ( Cs,ox) as a function of the sum of the activities of the oxalate and bioxalate in solution may be described by the general adsorption isotherm: C=6.1×10-7·{64·a}/{1+64·a}. The possible effect of oxalate on the proton-promoted dissolution rate was examined by comparing the results of the present study to literature

  14. 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...

  15. Use of Microfocused X-ray Techniques to Investigate the Mobilization of As by Oxalic Acid

    PubMed Central

    Wovkulich, Karen; Mailloux, Brian J.; Bostick, Benjamin C.; Dong, Hailiang; Bishop, Michael E.; Chillrud, Steven N.

    2012-01-01

    Improved linkages between aqueous phase transport and solid-phase reactions are needed to better predict and model transport of contaminants through the subsurface. Here we develop and apply a new method for measuring As mobilization in situ within soil columns that utilizes synchrotron-based X-ray fluorescence. By performing these measurements in situ during column transport experiments, we simultaneously monitor grain-scale solid phase reactions and column-scale transport. Arsenic may be effectively mobilized by oxalic acid but the geochemical and mineralogical factors that influence the rate and extent of mobilization are not well understood. Column experiments (~4 cm long × 0.635 cm ID) using As contaminated sediments from the Vineland Chemical Company Superfund site were performed on the laboratory bench as well as in the synchrotron beamline. Microfocused synchrotron X-ray fluorescence (μSXRF) maps for As and Fe were collected at the same location in the columns (<1 mm2) before and during treatment with 10 mM oxalic acid. The fraction of As and Fe removed by oxalic acid treatment was calculated from the change in flux-normalized counts for each pixel in the map images, and these data were used to calculate kinetic parameters over the studied area. Between 79% and 83% of the As was removed from the sediments by the oxalic acid treatment based on μSXRF data; these removal percentages agreed well with laboratory data based on column effluent (88–95%). Considerably less Fe was removed by oxalic acid treatment, 14–25% based on μSXRF counts, which is somewhat higher than the 7–9% calculated from laboratory column effluent concentrations. Microfocused X-ray absorption near edge spectroscopy (μXANES) on a subset of points indicates most of the Fe was oxidized and present as a mixture of goethite, hematite, and ferrihydrite on sand grain coatings. Treatment with oxalic acid led to subtle shifts in Fe (III) species following oxalic acid treatment, either

  16. Use of microfocused X-ray techniques to investigate the mobilization of arsenic by oxalic acid

    NASA Astrophysics Data System (ADS)

    Wovkulich, Karen; Mailloux, Brian J.; Bostick, Benjamin C.; Dong, Hailiang; Bishop, Michael E.; Chillrud, Steven N.

    2012-08-01

    Improved linkages between aqueous phase transport and solid-phase reactions are needed to better predict and model transport of contaminants through the subsurface. Here we develop and apply a new method for measuring As mobilization in situ within soil columns that utilizes synchrotron-based X-ray fluorescence. By performing these measurements in situ during column transport experiments, we simultaneously monitor grain-scale solid phase reactions and column-scale transport. Arsenic may be effectively mobilized by oxalic acid but the geochemical and mineralogical factors that influence the rate and extent of mobilization are not well understood. Column experiments (˜4 cm long × 0.635 cm ID) using As contaminated sediments from the Vineland Chemical Company Superfund site were performed on the laboratory bench as well as in the synchrotron beamline. Microfocused synchrotron X-ray fluorescence (μSXRF) maps for As and Fe were collected at the same location in the columns (<1 mm2) before and during treatment with 10 mM oxalic acid. The fraction of As and Fe removed by oxalic acid treatment was calculated from the change in flux-normalized counts for each pixel in the map images, and these data were used to calculate kinetic parameters over the studied area. Between 79% and 83% of the As was removed from the sediments by the oxalic acid treatment based on μSXRF data; these removal percentages agreed well with laboratory data based on column effluent (88-95%). Considerably less Fe was removed by oxalic acid treatment, 14-25% based on μSXRF counts, which is somewhat higher than the 7-9% calculated from laboratory column effluent concentrations. Microfocused X-ray absorption near edge spectroscopy (μXANES) on a subset of points indicates most of the Fe was oxidized and present as a mixture of goethite, hematite, and ferrihydrite on sand grain coatings. Treatment with oxalic acid led to subtle shifts in Fe (III) species following oxalic acid treatment, either removing

  17. Use of formulations based on choline chloride-malonic acid deep eutectic solvent for back end of line cleaning in integrated circuit fabrication

    NASA Astrophysics Data System (ADS)

    Taubert, Jenny

    Interconnection layers fabricated during back end of line processing in semiconductor manufacturing involve dry etching of a low-k material and deposition of copper and metal barriers to create copper/dielectric stacks. After plasma etching steps used to form the trenches and vias in the dielectric, post etch residues (PER) that consist of organic polymer, metal oxides and fluorides, form on top of copper and low-k dielectric sidewalls. Currently, most semiconductor companies use semi aqueous fluoride (SAF) based formulations containing organic solvent(s) for PER removal. Unfortunately, these formulations adversely impact the environmental health and safety (EHS) requirements of the semiconductor industry. Environmentally friendly "green" formulations, free of organic solvents, are preferred as alternatives to remove PER. In this work, a novel low temperature molten salt system, referred as deep eutectic solvent (DES) has been explored as a back end of line cleaning (BEOL) formulation. Specifically, the DES system comprised of two benign chemicals, malonic acid (MA) and choline chloride (CC), is a liquid at room temperature. In certain cases, the formulation was modified by the addition of glacial acetic acid (HAc). Using these formulations, selective removal of three types of PER generated by timed CF4/O2 etching of DUV PR films on Cu was achieved. Type I PER was mostly organic in character (fluorocarbon polymer type) and had a measured thickness of 160 nm. Type II PER was much thinner (25 nm) and consisted of a mixture of organic and inorganic compounds (copper fluorides). Further etching generated 17 nm thick Type III PER composed of copper fluorides and oxides. Experiments were also conducted on patterned structures. Cleaning was performed by immersing samples in a temperature controlled (30 or 40° C) double jacketed vessel for a time between 1 and 5 minutes. Effectiveness of cleaning was characterized using SEM, XPS and single frequency impedance measurements

  18. [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

  19. Evaluation of oxalate decarboxylase and oxalate oxidase for industrial applications.

    PubMed

    Cassland, Pierre; Sjöde, Anders; Winestrand, Sandra; Jönsson, Leif J; Nilvebrant, Nils-Olof

    2010-05-01

    Increased recirculation of process water has given rise to problems with formation of calcium oxalate incrusts (scaling) in the pulp and paper industry and in forest biorefineries. The potential in using oxalate decarboxylase from Aspergillus niger for oxalic acid removal in industrial bleaching plant filtrates containing oxalic acid was examined and compared with barley oxalate oxidase. Ten different filtrates from chemical pulping were selected for the evaluation. Oxalate decarboxylase degraded oxalic acid faster than oxalate oxidase in eight of the filtrates, while oxalate oxidase performed better in one filtrate. One of the filtrates inhibited both enzymes. The potential inhibitory effect of selected compounds on the enzymatic activity was tested. Oxalate decarboxylase was more sensitive than oxalate oxidase to hydrogen peroxide. Oxalate decarboxylase was not as sensitive to chlorate and chlorite as oxalate oxidase. Up to 4 mM chlorate ions, the highest concentration tested, had no inhibitory effect on oxalate decarboxylase. Analysis of the filtrates suggests that high concentrations of chlorate present in some of the filtrates were responsible for the higher sensitivity of oxalate oxidase in these filtrates. Oxalate decarboxylase was thus a better choice than oxalate oxidase for treatment of filtrates from chlorine dioxide bleaching. PMID:19763895

  20. Communication: Remarkable electrophilicity of the oxalic acid monomer: An anion photoelectron spectroscopy and theoretical study

    SciTech Connect

    Buonaugurio, Angela; Graham, Jacob; Buytendyk, Allyson; Bowen, Kit H. E-mail: kbowen@jhu.edu; Ryder, Matthew R. Gutowski, Maciej E-mail: kbowen@jhu.edu; Keolopile, Zibo G. E-mail: kbowen@jhu.edu; Haranczyk, Maciej

    2014-06-14

    Our experimental and computational results demonstrate an unusual electrophilicity of oxalic acid, the simplest dicarboxylic acid. The monomer is characterized by an adiabatic electron affinity and electron vertical detachment energy of 0.72 and 1.08 eV (±0.05 eV), respectively. The electrophilicity results primarily from the bonding carbon-carbon interaction in the singly occupied molecular orbital of the anion, but it is further enhanced by intramolecular hydrogen bonds. The well-resolved structure in the photoelectron spectrum is reproduced theoretically, based on Franck-Condon factors for the vibronic anion → neutral transitions.

  1. Manganese Peroxidase-Dependent Oxidation of Glyoxylic and Oxalic Acids Synthesized by Ceriporiopsis subvermispora Produces Extracellular Hydrogen Peroxide

    PubMed Central

    Urzúa, Ulises; Kersten, Philip J.; Vicuña, Rafael

    1998-01-01

    The ligninolytic system of the basidiomycete Ceriporiopsis subvermispora is composed of manganese peroxidase (MnP) and laccase. In this work, the source of extracellular hydrogen peroxide required for MnP activity was investigated. Our attention was focused on the possibility that hydrogen peroxide might be generated by MnP itself through the oxidation of organic acids secreted by the fungus. Both oxalate and glyoxylate were found in the extracellular fluid of C. subvermispora cultures grown in chemically defined media, where MnP is also secreted. The in vivo oxidation of oxalate was measured; 14CO2 evolution was monitored after addition of exogenous [14C]oxalate to cultures at constant specific activity. In standard cultures, evolution of CO2 from oxalate was maximal at day 6, although the MnP titers were highest at day 12, the oxalate concentration was maximal (2.5 mM) at day 10, and the glyoxylate concentration was maximal (0.24 mM) at day 5. However, in cultures containing low nitrogen levels, in which the pH is more stable, a better correlation between MnP titers and mineralization of oxalate was observed. Both MnP activity and oxidation of [14C]oxalate were negligible in cultures lacking Mn(II). In vitro assays confirmed that Mn(II)-dependent oxidation of [14C]oxalate by MnP occurs and that this reaction is stimulated by glyoxylate at the concentrations found in cultures. In addition, both organic acids supported phenol red oxidation by MnP without added hydrogen peroxide, and glyoxylate was more reactive than oxalate in this reaction. Based on these results, a model is proposed for the extracellular production of hydrogen peroxide by C. subvermispora. PMID:16349495

  2. 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

  3. COMPARISON OF OXALIC ACID CLEANING RESULTS AT SRS AND HANFORD AND THE IMPACT ON ENHANCED CHEMICAL CLEANING DEPLOYMENT

    SciTech Connect

    Spires, R.; Ketusky, E.

    2010-01-05

    Waste tanks must be rendered clean enough to satisfy very rigorous tank closure requirements. During bulk waste removal, most of the radioactive sludge and salt waste is removed from the waste tank. The waste residue on the tank walls and interior components and the waste heel at the bottom of the tank must be removed prior to tank closure to render the tank clean enough to meet the regulatory requirement for tank closure. Oxalic acid has been used within the DOE complex to clean residual materials from carbon steel tanks with varying degrees of success. Oxalic acid cleaning will be implemented at both the Savannah River Site and Hanford to clean tanks and serves as the core cleaning technology in the process known as Enhanced Chemical Cleaning. Enhanced Chemical Cleaning also employs a process that decomposes the spent oxalic acid solutions. The oxalic acid cleaning campaigns that have been performed at the two sites dating back to the 1980's are compared. The differences in the waste characteristics, oxalic acid concentrations, flushing, available infrastructure and execution of the campaigns are discussed along with the impact on the effectiveness of the process. The lessons learned from these campaigns that are being incorporated into the project for Enhanced Chemical Cleaning are also explored.

  4. Enzymatic Enantioselective Decarboxylative Protonation of Heteroaryl Malonates

    PubMed Central

    Lewin, Ross; Goodall, Mark; Thompson, Mark L; Leigh, James; Breuer, Michael; Baldenius, Kai; Micklefield, Jason

    2015-01-01

    The enzyme aryl/alkenyl malonate decarboxylase (AMDase) catalyses the enantioselective decarboxylative protonation (EDP) of a range of disubstituted malonic acids to give homochiral carboxylic acids that are valuable synthetic intermediates. AMDase exhibits a number of advantages over the non-enzymatic EDP methods developed to date including higher enantioselectivity and more environmentally benign reaction conditions. In this report, AMDase and engineered variants have been used to produce a range of enantioenriched heteroaromatic α-hydroxycarboxylic acids, including pharmaceutical precursors, from readily accessible α-hydroxymalonates. The enzymatic method described here represents an improvement upon existing synthetic chemistry methods that have been used to produce similar compounds. The relationship between the structural features of these new substrates and the kinetics associated with their enzymatic decarboxylation is explored, which offers further insight into the mechanism of AMDase. PMID:25766433

  5. 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.

  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. 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

  8. Malone appendicostomy: an unexpected complication.

    PubMed

    Abbes Orabi, N; Paterson, H M; Goncette, L; Danse, E; Saey, J P; Kartheuser, A

    2011-03-01

    The Malone appendicostomy is a novel option for surgical management of faecal incontinence and chronic constipation, by permitting the administration of antegrade colonic enemas for colonic evacuation. We report the case of a 54-year-old female who had undergone abdomino perineal resection for low rectal cancer followed by total perineal reconstruction with perineal colostomy, dynamic double graciloplasty and Malone appendicostomy. After 7-year follow-up, functional results and quality of life scores were satisfactory. Suddenly the patient described increasing difficulty with intubation of her appendicostomy and complete reflux of the enema liquid, which radiology referred to a calcified body of 35 mm within the Malone appendicostomy causing nearly complete obstruction of the conduit. A surgical exploration was necessary to extract the fecolith allowing full recovery with return to satisfactory Malone appendicostomy function. To our knowledge, this is the first report of a fecolith causing obstruction within a Malone appendicostomy. PMID:21287220

  9. 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. PMID:25897692

  10. Bioleaching of spent refinery processing catalyst using Aspergillus niger with high-yield oxalic acid.

    PubMed

    Santhiya, Deenan; Ting, Yen-Peng

    2005-03-16

    A spent refinery processing catalyst was physically and chemically characterized, and subjected to one-step and two-step bioleaching processes using Aspergillus niger. During bioleaching of the spent catalysts of various particle sizes ("as received", 100-150 microm, <37 microm, and x =2.97 (average) microm) and pulp densities, the biomass dry weight and pH were determined. The corresponding leach liquor was analysed for excreted organic acids along with heavy metal values extracted from the catalyst. Chemical characterization of the spent catalyst confirmed the presence of heavy metal including Al (33.3%), Ni (6.09%) and Mo (13.72%). In general, the presence of the spent catalyst caused a decrease in the biomass yield and an increase in oxalic acid secretion by A. niger. The increase in oxalic acid secretion with a decrease in the catalyst particle size (up to <37 microm) led to corresponding increase in the extraction of metal values. The highest extraction of metal values from the spent catalyst (at 1% w/v pulp density and particle size <37 microm) were found to be 54.5% Al, 58.2% Ni and 82.3% Mo in 60 days of bioleaching. Oxalic acid secretion by A. niger in the presence of the spent catalyst was stimulated using 2-[N-Morpholino]ethanesulfonic acid (MES) buffer (pH 6), which resulted in comparable metal extraction (58% Al, 62.8% Ni and 78.9% Mo) in half the time required by the fungus in the absence of the buffer. Spent medium of A. niger grown in the absence and in the presence of MES buffer were found to leach almost similar amounts of Al and Ni, except Mo for which the spent medium of buffered culture was significantly more effective than the non-buffered culture. Overall, this study shows the possible use of bioleaching for the extraction of metal resources from spent catalysts. It also demonstrated the advantages of buffer-stimulated excretion of organic acids by A. niger in bioleaching of the spent catalyst. PMID:15664081

  11. ISOLATED MEDICAGO TRUNCATULA MUTANTS WITH INCREASED CALCIUM OXALATE CRYSTAL ACCUMULATION HAVE DECREASED ASCORBIC ACID LEVELS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The mechanisms controlling oxalate biosynthesis and calcium oxalate formation in plants remains largely unknown. As an initial step toward gaining insight into these regulatory mechanisms we initiated a mutant screen to identify plants that over-accumulate crystals of calcium oxalate. Four new mut...

  12. Structure Determination and Refinement of Acid Strontium Oxalate from X-Ray and Neutron Powder Diffraction

    NASA Astrophysics Data System (ADS)

    Vanhoyland, G.; Bourée, F.; Van Bael, M. K.; Mullens, J.; Van Poucke, L. C.

    2001-03-01

    The structure of acid strontium oxalate Sr(HC2O4)·{1}/{2}(C2O4)·H2O has been determined by conventional X-ray powder diffractometry. The diffraction pattern was indexed from a monoclinic unit cell with cell parameters a=6.341(1) Å, b=16.880(2) Å, c=5.7798(8) Å, and β=97.60(1)°; space group, P21/n (No. 14) with Z=4. Final (isotropic) Rietveld refinement of the neutron powder data yielded RB=4.57%, RF=2.87%, and Rwp=7.87% as conventional Rietveld parameters. Strontium is eight-fold coordinated and can be described as a distorted bicapped trigonal prism. The SrO8 polyhedra form one-dimensional chains along the c-axis by sharing edges. In contrast to all other known strontium oxalates, in this compound H2O acts as bridging ligand between two Sr atoms. SDPD-D classification (1): Sr(HC2O4)-{1}/{2}(C2O4)-H2O, P21/n, C1=14, Nc=42, C2=11, XC1+N/TREOR-97 & DICVOL-91, EXTRA, EQUI, SIRPOW-92 (DM), GFOURIER, FULLPROF.

  13. 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.

  14. Conformational studies of aminomethylene-malonic acid dimethylester and its N-methyl derivatives using vibrational spectroscopy, X-ray analysis and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Gatial, A.; Matějka, P.; Kožíšek, J.; Milata, V.; Prónayová, N.

    2009-04-01

    The IR and Raman spectra of aminomethylene-malonic acid dimethylester (AMDME) [NH 2sbnd CH dbnd C(COOCH 3) 2] and its N-methyl derivatives (MAMDME and DMAMDME) were measured in solid phase and in different solvents at various temperatures. X-ray analysis revealed that AMDME exists in solid phase as EZ conformer, MAMDME as ZZa conformer and DMAMDME as ZE conformer (the first and second E or Z letters express the orientation of the carbonyl oxygen to the C dbnd C double bond for trans and cis methylester group, respectively, and the third letter a denotes anti position of methylamino group with respect to the C dbnd C double bond). In less polar solutions dominantly two ZZ and EZ conformational forms of AMDME and ZZa and EZa of MAMDME are observed, whereas in more polar environments a third conformational form ( ZE and ZEa, respectively) also appeared. The behaviour of DMAMDME is different because there is no intramolecular hydrogen bond and in less polar solutions exists in two ZZ and ZE conformational forms. Very weak indications of a third conformational form (probably EZ conformer) were observed only in more polar surroundings. From the solution IR temperature dependent spectra the energy difference between ZE and ZZ conformers of ΔH = 1.8 ± 0.5 kJ mol -1 in chloroform and ΔH = 4.2 ± 0.5 kJ mol -1 in acetonitrile was estimated with the ZZ one being more stable. The geometries and relative energies of the possible conformers of all three compounds were evaluated using ab initio MP2 and DFT B3LYP methods in 6-31G ∗∗ basis set with PCM solvent effect inclusion. The influence of environment polarity on the conformational equilibrium is discussed.

  15. Effect of oxalic acid pre-treatment in restorations of non-carious cervical lesions: A randomized clinical trial

    PubMed Central

    de Souza, André Mattos Brito; Colares, Regina Claudia Ramos; Mendonça, Juliano Satori; Rodrigues, Lidiany Karla Azevedo; Santiago, Sérgio Lima

    2014-01-01

    Context: Non-carious cervical lesions are usually associated with dentin hypersensitivity. The use of oxalic acid in restorations of these lesions could be beneficial in relieving pain. Aims: To evaluate the use of oxalic acid in restorations of non-carious cervical lesions. Settings and Design: A randomized clinical trial. Subjects and Methods: One operator placed 90 restorations in 20 volunteers of both sexes, with at least two lesions to be restored with the techniques: Control — Restoration with total-etch technique and Experimental — Restoration with pretreatment with oxalic acid followed by application of adhesive system. The restorative adhesive system used was XP Bond/Durafill. The restorations were directly assessed by two independent examiners using a modified United States Public Health Service (USPHS) method at baseline, 6 and 12 months, taking into account the following criteria: Retention (R), marginal integrity (MI), marginal discoloration (MD), postoperative sensitivity (S), caries (C), and anatomic form (AF). Statistical analysis used: The data were statistically analyzed using the Fisher exact and McNemar tests. The level of significance was set at 5%. Results: After 1 year, the results of restorations clinically satisfactory obtained for the control and experimental group respectively were: R (97% / 89%), MI (100% / 100%), MD (100% / 100%), S (100% / 100%), C (100% / 100%), and AF (100% / 100%). Conclusions: The use of oxalic acid as an agent of dentin pretreatment did not influence the clinical performance of restorations in non-carious cervical lesions after 1 year. PMID:25298641

  16. 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…

  17. Improved Thermoelectric Properties of PEDOT:PSS Nanofilms Treated with Oxalic Acid

    NASA Astrophysics Data System (ADS)

    Liu, Congcong; Shi, Hui; Xu, Jingkun; Jiang, Qinglin; Song, Haijun; Zhu, Zhengyou

    2015-06-01

    Poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) nanofilms were prepared by a simple spin-coating method. The thermoelectric properties of PEDOT:PSS nanofilms were improved by treatment with different concentrations of oxalic acid at 140°C. The electrical conductivity of PEDOT:PSS nanofilms can be improved from 0.48 to over 800 S cm-1, that is, by a factor of more than 1600 higher than for untreated PEDOT:PSS films. The Seebeck coefficient of the PEDOT:PSS nanofilms decreases slightly and the electrical conductivity increases. The maximum power factor of PEDOT:PSS nanofilms is up to 6.96 μW m-1 K-2. Atomic force microscopy and x-ray photoelectron spectroscopy were conducted to characterize the PEDOT:PSS nanofilms.

  18. Self-Ordered Nanoporous Alumina Templates Formed by Anodization of Aluminum in Oxalic Acid

    NASA Astrophysics Data System (ADS)

    Vida-Simiti, Ioan; Nemes, Dorel; Jumate, Nicolaie; Thalmaier, Gyorgy; Sechel, Niculina

    2012-10-01

    Anodic aluminum oxide (AAO) membranes with highly ordered nanopores serve as ideal templates for the formation of various nanostructured materials. The procedure of the template preparation is based on a two-step self-organized anodization of aluminum. In the current study, AAO templates were fabricated in 0.3 M oxalic acid under the anodizing potential range of 30-60 V at an electrolyte temperature of ~5°C. The AAO templates were analyzed using scanning electron microscopy, x-ray diffraction, Fourier-transform infrared spectroscopy, and differential thermal analysis. The as obtained layers are amorphous; the mean pore size is between 40 nm and 75 nm and increases with the increase of the anodization potential. Well-defined pores across the whole aluminum template, a pore density of ~1010 pores/cm2, and a tendency to form a porous structure with hexagonal symmetry were observed.

  19. Growth and characterization of urea-oxalic acid crystals by solution growth technique

    NASA Astrophysics Data System (ADS)

    Chithambaram, V.; Jerome Das, S.; Krishnan, Sivakumar; Basheer Ahamed, M.; Arivudai Nambi, R.

    2013-11-01

    Single crystals of urea-oxalic acid (UOA) have been grown from aqueous solution by slow evaporation technique. Single crystal X-ray diffraction analysis confirmed that the grown crystals belong to monoclinic system having space group P21/C. The presence of functional groups was confirmed by using Fourier transform infrared (FTIR) spectroscopy. Optical absorption studies show very low absorption in entire visible region and the UV cut-off is found to be around 240 nm. Thermal analysis studies were carried out using TG/DTA analysis and the grown crystal is thermally stable up to 180 °C. Dielectric constant studies confirm the ferroelectric property of the materials and very low dielectric loss reveals very high purity of the crystal.

  20. Experimental alkali feldspar dissolution at 100 degree C by carboxylic acids and their anions

    SciTech Connect

    Stoessell, R.K. ); Pittman, E.D. )

    1990-05-01

    Feldspar dissolution will enhance sandstone porosity if the released aluminum can be transported away in the subsurface waters. Carboxylic acids have been proposed to provide hydrogen ions to promote dissolution and anions to complex aqueous aluminum to keep it in solution. However, the hydrogen ions should react quickly following acid generation in source beds, leaving monocarboxylic anions with lesser amounts of dicarboxylic acids and their anions on feldspar dissolution and the apparent complexing of aluminum in solution. Two-week dissolution experiments of alkali feldspar were run at 100{degree}C and 300 bars in acetic acid, oxalic acid, and sodium salt solutions of chloride, acetate, propionate, oxalate, and malonate. Extrapolation of the results, to reservoir conditions during sandstone diagenesis, implies that concentrations of aluminum-organic complexes are not significant for acetate and propionate and are possibly significant for oxalate and malonate, depending upon fluid compositions. Propionate appeared to inhibit feldspar dissolution and hence might decrease secondary porosity formation. Increases in aluminum concentrations in the presence of oxalic and acetic acid solutions appear to be due to enhanced dissolution kinetics and greater aluminum solubility under low-pH conditions. Such low-pH fluids are generally absent in subsurface reservoirs, making this an unlikely mechanism for enhancing porosity. Furthermore, the observed thermal instability of oxalate and malonate anions explains their general low concentrations in subsurface fluids which limits their aluminum complexing potential in reservoirs during late diagenesis.

  1. 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...

  2. Improvement of the fermentability of oxalic acid hydrolysates by detoxification using electrodialysis and adsorption.

    PubMed

    Jeong, So-Yeon; Trinh, Ly Thi Phi; Lee, Hong-Joo; Lee, Jae-Won

    2014-01-01

    A two-step detoxification process consisting of electrodialysis and adsorption was performed to improve the fermentability of oxalic acid hydrolysates. The constituents of the hydrolysate differed significantly between mixed hardwood and softwood. Acetic acid and furfural concentrations were high in the mixed hardwood, whereas 5-hydroxymethylfurfural (HMF) concentration was relatively low compared with that of the mixed softwood. The removal efficiency of acetic acid reached 100% by electrodialysis (ED) process in both hydrolysates, while those of furfural and HMF showed very low, due to non-ionizable properties. Most of the remaining inhibitors were removed by XAD-4 resin. In the mixed hardwood hydrolysate without removal of the inhibitors, ethanol fermentation was not completed. Meanwhile, both ED-treated hydrolysates successfully produced ethanol with 0.08 and 0.15 g/Lh ethanol productivity, respectively. The maximum ethanol productivity was attained after fermentation with 0.27 and 0.35 g/Lh of detoxified hydrolysates, which were treated by ED, followed by XAD-4 resin. PMID:24321607

  3. 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

  4. Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies.

    PubMed

    Stare, Jernej; Hadži, Dušan

    2014-04-01

    The distance of ∼2.49 Å separating the carboxylic OH oxygen from the water oxygen atom in the α-polymorph of crystalline oxalic acid dihydrate is by ∼0.1 Å shorter than the average distance in carboxylic acid monohydrates. It is also by ∼0.2 Å shorter than the corresponding distance presently calculated for the heterotrimer consisting of one acid and two water molecules. The large difference between RO···O in the heterotrimer and in the crystal is attributed to the cooperative effect in the latter; this is supported by calculations carried out on clusters constituted of an increasing number of acid and water molecules. The present DFT calculations with geometry optimization include seven isolated model clusters, the largest of which contains five acid and eight water molecules. The RO···O of the short hydrogen bond shortens progressively with increasing the number of cluster constituents; in the largest cluster, it reaches 2.50 Å. This is remarkably close to both the experimental distance as well as to the distance obtained by the periodic DFT calculation. The electronic effects were studied by Natural Bond Orbital analysis, revealing an enhancement of hydrogen bonding on extending the network by increased polarization of the carbonyl group and by the increased delocalization interaction between the lone electron pair on the acceptor oxygen atom and the OH antibond orbital. The formation of circular motifs appears to be the most important factor in the cooperative shortening of the hydrogen bonds. In agreement with the measured hydrogen bond distances, inspection of the electron density reveals a notable difference in hydrogen bond shrinking tendency between the two known polymorphs of the title system. PMID:26580388

  5. 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.

  6. Hippuric Acid as a Significant Regulator of Supersaturation in Calcium Oxalate Lithiasis: The Physiological Evidence

    PubMed Central

    Atanassova, Stoyanka S.; Gutzow, Ivan S.

    2013-01-01

    At present, the clinical significance of existing physicochemical and biological evidence and especially the results we have obtained from our previous in vitro experiments have been analyzed, and we have come to the conclusion that hippuric acid (C6H5CONHCH2COOH) is a very active solvent of Calcium Oxalate (CaOX) in physiological solutions. Two types of experiments have been discussed: clinical laboratory analysis on the urine excretion of hippuric acid (HA) in patients with CaOX lithiasis and detailed measurements of the kinetics of the dissolution of CaOX calculi in artificial urine, containing various concentrations of HA. It turns out that the most probable value of the HA concentration in the control group is approximately ten times higher than the corresponding value in the group of the stone-formers. Our in vitro analytical measurements demonstrate even a possibility to dissolve CaOX stones in human urine, in which increased concentration of HA have been established. A conclusion can be that drowning out HA is a significant regulator of CaOX supersaturation and thus a regulation of CaOX stone formation in human urine. Discussions have arisen to use increased concentration of HA in urine both as a solubilizator of CaOX stones in the urinary tract and on the purpose of a prolonged metaphylactic treatment. PMID:24307993

  7. 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.

  8. Non-enzymatic oxalic acid sensor using platinum nanoparticles modified on graphene nanosheets

    NASA Astrophysics Data System (ADS)

    Chen, Xiaomei; Cai, Zhixiong; Huang, Zhiyong; Oyama, Munetaka; Jiang, Yaqi; Chen, Xi

    2013-06-01

    An enzyme-free oxalic acid (OA) electrochemical sensor was assembled using a platinum nanoparticle-loaded graphene nanosheets (PtNPGNs)-modified electrode. The PtNPGNs, with a high yield of PtNPs dispersed on the graphene nanosheets, were successfully achieved by a green, rapid, one-step and template-free method. The resulting PtNPGNs were characterized by transmission electron microscopy (TEM), high-resolution TEM, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and an X-ray diffraction technique. Electrochemical oxidation of OA on the PtNPGNs-modified electrode was investigated by cyclic voltammetry and differential pulse voltammetry methods. Based on the results, the modified electrode exhibited high electrochemical activity with well-defined peaks of OA oxidation and a notably decreased overpotential compared to the bare or even the GNs-modified electrode. Under optimized conditions, a good linear response was observed for the concentration of OA and its current response was in the range of 0.1-15 mM and 15-50 mM with a detection limit (S/N = 3) of 10 μM. Furthermore, the electrochemical sensor presented good characteristics in terms of stability and reproducibility, promising the applicability of the sensor in practical analysis.An enzyme-free oxalic acid (OA) electrochemical sensor was assembled using a platinum nanoparticle-loaded graphene nanosheets (PtNPGNs)-modified electrode. The PtNPGNs, with a high yield of PtNPs dispersed on the graphene nanosheets, were successfully achieved by a green, rapid, one-step and template-free method. The resulting PtNPGNs were characterized by transmission electron microscopy (TEM), high-resolution TEM, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and an X-ray diffraction technique. Electrochemical oxidation of OA on the PtNPGNs-modified electrode was investigated by cyclic voltammetry and differential pulse voltammetry methods. Based on the results, the modified

  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. 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. PMID:22849190

  11. Polishing of InSb in K2Cr2O7-HBr-HCl (oxalic acid) solutions

    NASA Astrophysics Data System (ADS)

    Tomashik, V. N.; Kusiak, N. V.; Tomashik, Z. F.; Danylenko, S. G.

    2001-02-01

    Dissolution of InAs in the K2Cr2O7-HBr-HCl (oxalic acid) solutions is studied in reproducible hydrodynamics conditions. The surfaces of equal etching rate are constructed using mathematical planning of experiment, and the limiting stages of the dissolution process are determined. The kinetic behavior of indicated semiconductors depending on the mixing rate and temperature of solution was investigated and it was shown that the dissolution of these semiconductor compounds in the solutions of the investigated systems is limited by the diffusion stages. The dissolution rates of InSb in such solutions distinguish weakly from each other and are within the interval of 0.5 - 6 micrometer/min. The solutions of K2Cr2O7-HBr-HCl (oxalic acid) systems can be employed for the developing of polishing solutions for the indium antimonide treatment with small etching rate.

  12. Effects of acid-base variables and the role of carbonic anhydrase on oxalate secretion by the mouse intestine in vitro

    PubMed Central

    Whittamore, Jonathan M; Frost, Susan C; Hatch, Marguerite

    2015-01-01

    Hyperoxaluria is a major risk factor for calcium oxalate kidney stones and the intestine is recognized as an important extra-renal pathway for eliminating oxalate. The membrane-bound chloride/bicarbonate (Cl−/) exchangers are involved in the transcellular movement of oxalate, but little is understood about how they might be regulated. , CO2, and pH are established modulators of intestinal NaCl cotransport, involving Na+/H+ and Cl−/ exchange, but their influence on oxalate transport is unknown. Measuring 14C-oxalate and 36Cl fluxes across isolated, short-circuited segments of the mouse distal ileum and distal colon we examined the role of these acid-base variables and carbonic anhydrase (CA) in oxalate and Cl− transport. In standard buffer both segments performed net oxalate secretion (and Cl− absorption), but only the colon, and the secretory pathway were responsive to and CO2. Ethoxzolamide abolished net oxalate secretion by the distal colon, and when used in tandem with an impermeant CA inhibitor, signaled an intracellular CA isozyme was required for secretion. There was a clear dependence on as their removal eliminated secretion, while at 42 mmol/L was also decreased and eradicated. Independent of pH, raising Pco2 from 28 to 64 mmHg acutely stimulated net oxalate secretion 41%. In summary, oxalate secretion by the distal colon was dependent on , CA and specifically modulated by CO2, whereas the ileum was remarkably unresponsive. These findings highlight the distinct segmental heterogeneity along the intestine, providing new insights into the oxalate transport mechanism and how it might be regulated. PMID:25716924

  13. 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

  14. 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

  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. PMID:27441258

  16. 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., Jr.

    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.

  17. 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)

  18. Contrasting Effects of Water on the Barriers to Decarboxylation of Two Oxalic Acid Monohydrates: A Combined Rotational Spectroscopic and Ab Initio Study.

    PubMed

    Schnitzler, Elijah G; Badran, Courtenay; Jäger, Wolfgang

    2016-04-01

    Using rotational spectroscopy, we have observed two isomers of the monohydrate of oxalic acid, the most abundant dicarboxylic acid in the atmosphere. In the lowest-energy isomer, water hydrogen-bonds to both carboxylic acid groups, and the barrier to decarboxylation decreases. In the second isomer, water bonds to only one carboxylic acid group, and the barrier increases. Though the lower barrier in the former is not unequivocal evidence that water acts as a photocatalyst, the higher barrier in the latter indicates that water acts as an inhibitor in this topology. Oxalic acid is unique among dicarboxylic acids: for the higher homologues calculated, the inhibiting topology of the monohydrate is lowest in energy and most abundant under atmospheric conditions. Consequently, oxalic acid is the only dicarboxylic acid for which single-water catalysis of overtone-induced decarboxylation in the atmosphere is plausible. PMID:26963633

  19. Size distributions and formation of dicarboxylic acids in atmospheric particles

    NASA Astrophysics Data System (ADS)

    Yao, Xiaohong; Fang, Ming; Chan, Chak K.

    The PM2.5 concentrations and the size distributions of dicarboxylic acids in Hong Kong were studied. Eleven sets of daily PM2.5 samples were obtained at a downtown sampling site during the period of 5-16 December 2000 using an R&P speciation PM2.5 sampler. About 6-12% of the total oxalic acid was found in the gas phase in some samples. A good correlation between succinate and sulfate ( R2=0.88) and a moderate correlation between oxalate and sulfate ( R2=0.74) were found. Sampling artifacts of oxalate, malonate and succinate were found to be negligible. A total of 18 sets of 48-96 h size distribution data on dicarboxylic acids, sulfate, nitrate and sodium at an urban site and a rural site from June 2000 to May 2001 were obtained using a Micro-Orifice Uniform Deposit Impactor. Data from both sites show similar size distribution characteristics of the dicarboxylic acids. The condensation mode of oxalate was usually observed at 0.177-0.32 μm. The location of the peak of the droplet mode of oxalate was associated with that of sulfate. When the peak of sulfate in the droplet mode appeared at 0.32-0.54 μm, the peak of oxalate sometimes appeared at 0.32-0.54 μm and sometimes shifted to 0.54-1.0 μm. When the peak of sulfate in the droplet mode appeared at 0.54-1.0 μm, the peak of oxalate sometimes appeared at 0.54-1.0 μm and sometimes shifted to 1.0-1.8 μm. Oxalate, succinate and sulfate found in the droplet mode were attributed to in-cloud formation. The slight shift of the oxalate peak from 0.32-0.54 to 0.54-1.0 μm or from 0.54-1.0 to 1.0-1.8 μm was ascribed to minor oxalate evaporation after in-cloud formation. The maximum peak of malonate sometimes appeared in the droplet mode and sometimes appeared at 3.1-6.2 μm. The formation of malonate is associated to the reactions between sea salt and malonic acid.

  20. Self-assembly of silver(I) coordination polymers from aminopyrimidyl derivatives and malonate acid: From 1D chain to 2D layer

    NASA Astrophysics Data System (ADS)

    Sun, Di; Zhang, Na; Xu, Qin-Juan; Luo, Geng-Geng; Huang, Rong-Bin; Zheng, Lan-Sun

    2010-04-01

    Two new silver(I) coordination polymers (CPs) of the formula [Ag 2(dmapym) 4(mal)·H 2O] n ( 1) and [Ag 3(apym) 3(mal)NO 3] n ( 2) (dmapym = 2-amino-4,6-dimethylprimidine, apym = 2-aminopyrimidine, H 2mal = malonate) have been synthesized by reactions of AgNO 3 and 2-aminopyrimidyl ligands with malonate under the ammoniacal condition. Both complexes have been characterized by element analysis, IR and single-crystal X-ray diffraction. The monodentate dmapym and tridentate mal ligands link Ag(I) ions to give complex 1 a one-dimensional (1D) H-shaped chain structure. The complex 2 is a two-dimensional (2D) double sheet structure constructed by (4, 4) single sheet. Additionally, the hydrogen-bonding and C-H⋯π interactions also direct the self-assembly of supramolecular architectures. The photoluminescence properties of the 1 and 2 were investigated in the solid state at room temperature.

  1. 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.

  2. 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.

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

    PubMed Central

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

    2015-01-01

    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. PMID:25675494

  4. 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. PMID:25675494

  5. Evidence for 13-carbon enrichment in oxalic acid via iron catalyzed photolysis in aqueous phase

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka

    2012-02-01

    To investigate the effect of photochemical aging on the stable carbon isotopic ratio (δ13C) of oxalic acid (OxA), a dominant organic species in atmospheric aerosols, we conducted a laboratory photolysis of OxA under H2O2-Fe3+(Fe2+)-UV system in aqueous phase and measured δ13C of remaining OxA. Our results showed that a significant photolysis of OxA occurred with OH radical but the isotopic fractionation of OxA was insignificant. In contrast, in the presence of Fe3+ (Fe2+), we found a significant enrichment of 13C in remaining OxA. We also found that kinetic isotope effect (KIE) of OxA largely depends on photochemical age (irradiation time) and concentration ratios of OxA to iron; 3.20 ± 0.49‰ (2.18 ± 1.18‰) and 21.62 ± 5.41‰ in 90 min and 180 min irradiation, in which OxA and Fe3+ (Fe2+) ratios were 50:1 and 200:1, respectively. The enrichment of 13C in remaining OxA was more significant during the photolysis catalyzed by Fe3+ (7‰) than by Fe2+ (3‰) in 90 min irradiation when OxA and iron ratios are the same (50:1). This study provides a laboratory evidence for the isotopic enrichment of 13C in OxA with photochemical aging. This approach is useful for better interpretation of atmospheric isotopic measurements in terms of the extent of atmospheric processing of aerosols.

  6. Ascorbate metabolism and the developmental demand for tartaric and oxalic acids in ripening grape berries

    PubMed Central

    2009-01-01

    Background Fresh fruits are well accepted as a good source of the dietary antioxidant ascorbic acid (Asc, Vitamin C). However, fruits such as grapes do not accumulate exceptionally high quantities of Asc. Grapes, unlike most other cultivated fruits do however use Asc as a precursor for the synthesis of both oxalic (OA) and tartaric acids (TA). TA is a commercially important product in the wine industry and due to its acidifying effect on crushed juice it can influence the organoleptic properties of the wine. Despite the interest in Asc accumulation in fruits, little is known about the mechanisms whereby Asc concentration is regulated. The purpose of this study was to gain insights into Asc metabolism in wine grapes (Vitis vinifera c.v. Shiraz.) and thus ascertain whether the developmental demand for TA and OA synthesis influences Asc accumulation in the berry. Results We provide evidence for developmentally differentiated up-regulation of Asc biosynthetic pathways and subsequent fluctuations in Asc, TA and OA accumulation. Rapid accumulation of Asc and a low Asc to dehydroascorbate (DHA) ratio in young berries was co-ordinated with up-regulation of three of the primary Asc biosynthetic (Smirnoff-Wheeler) pathway genes. Immature berries synthesised Asc in-situ from the primary pathway precursors D-mannose and L-galactose. Immature berries also accumulated TA in early berry development in co-ordination with up-regulation of a TA biosynthetic gene. In contrast, ripe berries have up-regulated expression of the alternative Asc biosynthetic pathway gene D-galacturonic acid reductase with only residual expression of Smirnoff-Wheeler Asc biosynthetic pathway genes and of the TA biosynthetic gene. The ripening phase was further associated with up-regulation of Asc recycling genes, a secondary phase of increased accumulation of Asc and an increase in the Asc to DHA ratio. Conclusion We demonstrate strong developmental regulation of Asc biosynthetic, recycling and catabolic

  7. 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.

  8. 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. PMID:25499499

  9. 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

  10. LC-MS analysis of low molecular weight organic acids derived from root exudation.

    PubMed

    Jaitz, Leonhard; Mueller, Bernhard; Koellensperger, Gunda; Huber, Daniela; Oburger, Eva; Puschenreiter, Markus; Hann, Stephan

    2011-06-01

    A sensitive method for quantification of citric, fumaric, malic, malonic, oxalic, trans aconitic, and succinic acid in soil- and root-related samples is presented. The method is based on a novel, fast, and simple esterification procedure and subsequent analysis via liquid chromatography-mass spectrometry. Derivatization comprises in situ generation of HCl, which catalyzes the Fischer esterification with benzyl alcohol. As a key advance, the esterification with the aromate allows reversed-phase separation and improves electrospray ionization efficiency. The method provided procedural detection limits of 1 nM for citric, 47 nM for fumaric, 10 nM for malic, 10 nM for malonic, 16 nM for oxalic, 15 nM for succinic, and 2 nM for aconitic acid utilizing 500 μL of liquid sample. The working range was 3 nM to 10 μM for citric acid, 158 nM to 10 μM for fumaric acid, 34 nM to 10 μM for malic acid, 33 nM to 10 μM for malonic acid, 53 nM to 10 μM for oxalic acid, 48 nM to 10 μM for succinic acid, and 6 nM to 10 μM for aconitic acid. Quantification of the analytes in soil-related samples was performed via external calibration of the entire procedure utilizing (13)C-labeled oxalic and citric acid as internal standards. The robustness of the method was tested with soil extracts and samples from hydroponic experiments. The latter concerned the regulation of phosphorus solubilization via plant root exudation of citric, malic, and oxalic acid. PMID:20711769

  11. 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. PMID:24920251

  12. Synthesis and characterization of nanocrystalline nickel oxide using NaOH and oxalic acid as oxide sources

    NASA Astrophysics Data System (ADS)

    Sathishkumar, K.; Shanmugam, N.; Kannadasan, N.; Cholan, S.; Viruthagiri, G.

    2014-04-01

    Precursors of nickel oxide (NiO) nanoparticles were synthesized through a simple chemical precipitation method by changing the oxide source used for the synthesis. The synthesized precursors were subjected to thermo gravimetric analysis (TGA) to determine the temperature at which the precursors decompose into nickel oxide. The obtained results of TGA suggest that precursor NiO prepared using sodium hydroxide (NaOH) showed NiO formation at 600 °C, whereas, when oxalic acid was used as oxide source the formation of NiO took place at 400 °C. After calcinations of the precursors at respective temperatures, NiO nanocrystals have been harvested. The synthesized NiO powders were characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectroscopy, field emission scanning electron microscopy (FE-SEM), energy dispersive x-ray analysis (EDX), and vibrating sample magnetometer (VSM) analysis. An FE-TEM image of NiO prepared using oxalic acid showed spherical and elliptical particles with sizes in the range of 15 nm. The Williamson-Hall (W-H) plots were drawn for the annealed products to study their lattice strain and crystallite size. The sizes of NiO nanocrystals obtained from W-H analysis are well correlated with sizes estimated using Scherrer’s formula. The relatively low saturation magnetization of NiO confirms its super paramagnetic behavior.

  13. Influence of oxalic acid on the agglomeration process and total soda content in precipitated Al(OH) 3

    NASA Astrophysics Data System (ADS)

    Nikolić, I.; Blec̆ić, D.; Blagojević, N.; Radmilović, V.; Kovac̆ević, K.

    2003-05-01

    Decomposition of caustic soda solutions is an important part of Bayer process for alumina production. The physico-chemical properties of precipitated Al(OH) 3 are dependent on several processes that take place simultaneously during the decomposition process and they are: nucleation, agglomeration and Al(OH) 3 crystals. An important industrial requirement is increase of Al(OH) 3 crystal grain size, and hence agglomeration and growth of Al(OH) 3 crystals become important processes and they enable increase of particle size. The influence of oxalic acid concentration on the agglomeration process and total soda content in precipitated Al(OH) 3 at different temperatures and caustic soda concentrations has been investigated. The results have shown that the agglomeration process is increased with increase of temperature and decrease of caustic soda concentration. Total soda content in precipitated Al(OH) 3 is changed in the same way. Besides, agglomeration process of Al(OH) 3 particles is favored in the presence of oxalic acid.

  14. 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.

  15. 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.

  16. Oxalic acid under adhesive restorations as a means to reduce dentin sensitivity: a four-month clinical trial.

    PubMed

    Barrientos, Claudia; Xaus, Gloria; Leighton, Catherine; Martin, Javier; Gordan, Valeria V; Moncada, Gustavo

    2011-01-01

    The aim of this double-blind randomized controlled clinical trial was to evaluate the reduction of dentin sensitivity using an oxalate-based compound, placed under adhesive restorations, during a four-month period. One hundred three preoperatively sensitive teeth, on 36 patients aged 25-66 years (mean, 40.3±7), were included in the study. Group A (experimental) was treated with oxalic acid (BisBlock) before resin-based composite (RBC) restorations (n=52), and group B (control) was treated with distilled water before RBC restorations (n=51). The first tooth in each patient was randomly assigned to group A, and the second tooth received group B. Clinical evaluation as made by a thermal/evaporation test with an air syringe and measurement by visual analog scale (VAS) at baseline and four months after treatment. The results showed sensitivity reduction during the evaluation period (expressed in VAS values): group A, 7.6 to 0.8; group B, 7.3 to 2.6. We concluded from this study that both treatments reduced dentin sensitivity during the evaluation period, with group A showing significantly less dentin sensitivity after four months (p<0.05). PMID:21777095

  17. 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. PMID:17623369

  18. 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

  19. Oxalate content of cereals and cereal products.

    PubMed

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

    2006-04-19

    Detailed knowledge of food oxalate content is of essential importance for dietary treatment of recurrent calcium oxalate urolithiasis. Dietary oxalate can contribute considerably to the amount of urinary oxalate excretion. Because cereal foods play an important role in daily nutrition, the soluble and total oxalate contents of various types of cereal grains, milling products, bread, pastries, and pasta were analyzed using an HPLC-enzyme-reactor method. A high total oxalate content (>50 mg/100 g) was found in whole grain wheat species Triticum durum (76.6 mg/100 g), Triticum sativum (71.2 mg/100 g), and Triticum aestivum (53.3 mg/100 g). Total oxalate content was comparably high in whole grain products of T. aestivum, that is, wheat flakes and flour, as well as in whole grain products of T. durum, that is, couscous, bulgur, and pasta. The highest oxalate content was demonstrated for wheat bran (457.4 mg/100 g). The higher oxalate content in whole grain than in refined grain cereals suggests that oxalic acid is primarily located in the outer layers of cereal grains. Cereals and cereal products contribute to the daily oxalate intake to a considerable extent. Vegetarian diets may contain high amounts of oxalate when whole grain wheat and wheat products are ingested. Recommendations for prevention of recurrence of calcium oxalate stone disease have to take into account the oxalate content of these foodstuffs. PMID:16608223

  20. 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.

  1. 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)

  2. Pre-storage application of oxalic acid alleviates chilling injury in mango fruit by modulating proline metabolism and energy status under chilling stress.

    PubMed

    Li, Peiyan; Zheng, Xiaolin; Liu, Yan; Zhu, Yuyan

    2014-01-01

    Effects of oxalic acid on chilling injury, proline metabolism and energy status in mango fruit were investigated after mango fruit (Mangifera indica L. cv. Zill) were dipped in 5mM oxalic acid solution for 10min at 25°C and then stored at low temperature (10±0.5°C) for 49days thereafter transferred to 25°C for 4days. Pre-storage application of oxalic acid apparently inhibited the development of chilling injury, notably elevated proline accumulation actually associated with increase in Δ(1)-pyrroline-5-carboxylate synthetase (P5CS) activity and decrease in proline dehydrogenase (PDH) activity in the peel and the flesh, without activation of ornithine-δ-aminotransferase (OAT) activity, and maintained high ATP level and energy charge in the flesh during storage. It was suggested that these effects of oxalic acid might collectively contribute to improving chilling tolerance, thereby alleviating chilling injury and maintaining quality of mango fruit in long term cold storage. PMID:24001814

  3. 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.

  4. 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. PMID:17931951

  5. Mechanistic insight into chromium(VI) reduction by oxalic acid in the presence of manganese(II).

    PubMed

    Wrobel, Katarzyna; Corrales Escobosa, Alma Rosa; Gonzalez Ibarra, Alan Alexander; Mendez Garcia, Manuel; Yanez Barrientos, Eunice; Wrobel, Kazimierz

    2015-12-30

    Over the past few decades, reduction of hexavalent chromium (Cr(VI)) has been studied in many physicochemical contexts. In this research, we reveal the mechanism underlying the favorable effect of Mn(II) observed during Cr(VI) reduction by oxalic acid using liquid chromatography with spectrophotometric diode array detector (HPLC-DAD), nitrogen microwave plasma atomic emission spectrometry (HPLC-MP-AES), and high resolution mass spectrometry (ESI-QTOFMS). Both reaction mixtures contained potassium dichromate (0.67 mM Cr(VI)) and oxalic acid (13.3mM), pH 3, one reaction mixture contained manganese sulfate (0.33 mM Mn(II)). In the absence of Mn(II) only trace amounts of reaction intermediates were generated, most likely in the following pathways: (1) Cr(VI)→ Cr(IV) and (2) Cr(VI)+Cr(IV)→ 2Cr(V). In the presence of Mn(II), the active reducing species appeared to be Mn(II) bis-oxalato complex (J); the proposed reaction mechanism involves a one-electron transfer from J to any chromium compound containing CrO bond, which is reduced to CrOH, and the generation of Mn(III) bis-oxalato complex (K). Conversion of K to J was observed, confirming the catalytic role of Mn(II). Since no additional acidification was required, the results obtained in this study may be helpful in designing a new, environmentally friendly strategy for the remediation of environments contaminated with Cr(VI). PMID:26177490

  6. 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.

  7. 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.

  8. 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.

    PubMed

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

    2015-06-15

    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/cm(2), an open circuit photo voltage (VOC) of 0.59 V and a fill factor of 0.44 under AM 1.5 illumination (85 mW/cm(2)) compared to diphenylamine based device. PMID:25801442

  9. Simple theory of a Malone engine

    NASA Astrophysics Data System (ADS)

    Swift, G. W.

    Practical liquid engines called Malone engines use a regenerative or recuperative cycle, like the Stirling cycle. A theoretical model of the Malone engine that is realistic enough for comparison to experiment, yet still simple enough for intuitive grasp of the engine's features, is presented. The principal results obtained with the model are the time-averaged heat and work resulting from each of the most important effects taking place in the engine. It is shown that Rankine heat pumps and Malone heat pumps with equal heat-pumping capabilities require compressors of comparable volumetric flow rates and hence of comparable complexity and size, but the heat exchangers for the Malone heat pump are expected to be orders of magnitude smaller than those for the Rankine-cycle heat pump.

  10. 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.

  11. 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

  12. Five year evaluation of class III composite resin restorations in cavities pre-treated with an oxalic- or a phosphoric acid conditioner.

    PubMed

    van Dijken, J W; Olofsson, A L; Holm, C

    1999-05-01

    An oxalic acid solution has been proposed as a conditioning agent for resin composite restorations in two commercial adhesive systems. The durability of 163 class III restorations, including 12 class IV restorations, in cavities pre-treated with an oxalic acid total etch technique or an enamel etch with phosphoric acid was studied. Each of 52 patients received at least one of each of three experimental restorations. The restorations were evaluated yearly with slightly modified United States Public Health Service (USPHS) criteria. After 5 years 95% of the restorations were evaluated as acceptable. Reasons for failure were the fracture of four fillings, including three class IV, secondary caries contiguous to two fillings and a non-acceptable colour match for one restoration. For eight class III restorations a fracture of the incisal tooth structure was registered. No differences were seen between the three experimental restorations. PMID:10373082

  13. Influence of anodization parameters on the volume expansion of anodic aluminum oxide formed in mixed solution of phosphoric and oxalic acids

    NASA Astrophysics Data System (ADS)

    Kao, Tzung-Ta; Chang, Yao-Chung

    2014-01-01

    The growth of anodic alumina oxide was conducted in the mixed solution of phosphoric and oxalic acids. The influence of anodizing voltage, electrolyte temperature, and concentration of phosphoric and oxalic acids on the volume expansion of anodic aluminum oxide has been investigated. Either anodizing parameter is chosen to its full extent of range that allows the anodization process to be conducted without electric breakdown and to explore the highest possible volume expansion factor. The volume expansion factors were found to vary between 1.25 and 1.9 depending on the anodizing parameters. The variation is explained in connection with electric field, ion transport number, temperature effect, concentration, and activity of acids. The formation of anodic porous alumina at anodizing voltage 160 V in 1.1 M phosphoric acid mixed with 0.14 M oxalic acid at 2 °C showed the peak volume expansion factor of 1.9 and the corresponding moderate growth rate of 168 nm/min.

  14. 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.

  15. 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

  16. Origin of Urinary Oxalate

    NASA Astrophysics Data System (ADS)

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

    2007-04-01

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

  17. Analysis of nanopore arrangement of porous alumina layers formed by anodizing in oxalic acid at relatively high temperatures

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    Anodic aluminum oxide (AAO) layers were formed by a simple two-step anodization in 0.3 M oxalic acid at relatively high temperatures (20-30 °C) and various anodizing potentials (30-65 V). The effect of anodizing conditions on structural features of as-obtained oxides was carefully investigated. A linear and exponential relationships between cell diameter, pore density and anodizing potential were confirmed, respectively. On the other hand, no effect of temperature and duration of anodization on pore spacing and pore density was found. Detailed quantitative and qualitative analyses of hexagonal arrangement of nanopore arrays were performed for all studied samples. The nanopore arrangement was evaluated using various methods based on the fast Fourier transform (FFT) images, Delaunay triangulations (defect maps), pair distribution functions (PDF), and angular distribution functions (ADF). It was found that for short anodizations performed at relatively high temperatures, the optimal anodizing potential that results in formation of nanostructures with the highest degree of pore order is 45 V. No direct effect of temperature and time of anodization on the nanopore arrangement was observed.

  18. 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

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

    DOE PAGESBeta

    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. An acidic peptide sequence of nucleolin-related protein can mediate the attachment of calcium oxalate to renal tubule cells.

    PubMed

    Sorokina, Elena A; Wesson, Jeffrey A; Kleinman, Jack G

    2004-08-01

    Crystals that form in tubular fluid must be retained in the kidney to become stones. Nucleolin-related protein (NRP) is found on the surface of inner medullary collecting duct (IMCD) cells in culture (cIMCD) and selectively adsorbs to calcium oxalate (CaOx). We proposed that NRP mediates attachment to the renal tubular epithelium of Ca stone crystals through an electrostatic interaction with a highly acidic region (acidic fragment [AF]) similar to those of other proteins that have been reported to affect urinary crystal formation. The current studies demonstrate that nucleolin is expressed on both apical and basolateral cell surfaces of cIMCD, reaching a peak in the late stages of mitosis and gradually declining to undetectable levels with maturation of the polarized epithelium. Scraping areas of mature monolayers stimulated the cells surrounding the defects to migrate and proliferate so as to repair them, and these areas demonstrate surface NRP expression and enhanced attachment of CaOx monohydrate crystals. Surface expression of the NRP AF was produced by cloning the NRP AF into a display vector. Transfected cIMCD demonstrating copious surface expression of AF enhanced CaOx attachment 6.7-fold compared with control cIMCD, whereas cells transfected with a vector without the AF did not differ from control. AF was also cloned into a replication-deficient adenovirus and expressed in 293 cells, resulting in AF secretion into the nutrient medium. This medium inhibited CaOx attachment to cIMCD, compared with conditioned medium from cells infected with wild-type virus. These results demonstrate that surface-bound AF can mediate CaOx attachment and that secreted AF can inhibit attachment. These results support the notion that surface-associated NRP could mediate attachment of CaOx to the renal tubule epithelium, thereby causing retention of crystals that might eventually become kidney stones. PMID:15284292

  1. 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.

  2. Nanouric acid or nanocalcium phosphate as central nidus to induce calcium oxalate stone formation: a high-resolution transmission electron microscopy study on urinary nanocrystallites

    PubMed Central

    Gao, Jie; Xue, Jun-Fa; Xu, Meng; Gui, Bao-Song; Wang, Feng-Xin; Ouyang, Jian-Ming

    2014-01-01

    Purpose This study aimed to accurately analyze the relationship between calcium oxalate (CaOx) stone formation and the components of urinary nanocrystallites. Method High-resolution transmission electron microscopy (HRTEM), selected area electron diffraction, fast Fourier transformation of HRTEM, and energy dispersive X-ray spectroscopy were performed to analyze the components of these nanocrystallites. Results The main components of CaOx stones are calcium oxalate monohydrate and a small amount of dehydrate, while those of urinary nanocrystallites are calcium oxalate monohydrate, uric acid, and calcium phosphate. The mechanism of formation of CaOx stones was discussed based on the components of urinary nanocrystallites. Conclusion The formation of CaOx stones is closely related both to the properties of urinary nanocrystallites and to the urinary components. The combination of HRTEM, fast Fourier transformation, selected area electron diffraction, and energy dispersive X-ray spectroscopy could be accurately performed to analyze the components of single urinary nanocrystallites. This result provides evidence for nanouric acid and/or nanocalcium phosphate crystallites as the central nidus to induce CaOx stone formation. PMID:25258530

  3. 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.

  4. Atomically mixed Fe-group nanoalloys: catalyst design for the selective electrooxidation of ethylene glycol to oxalic acid.

    PubMed

    Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Ozawa, Nobuki; Kubo, Momoji; Yamauchi, Miho

    2015-05-01

    We demonstrate electric power generation via the electrooxidation of ethylene glycol (EG) on a series of Fe-group nanoalloy (NA) catalysts in alkaline media. A series of Fe-group binary NA catalysts supported on carbon (FeCo/C, FeNi/C, and CoNi/C) and monometallic analogues (Fe/C, Co/C, and Ni/C) were synthesized. Catalytic activities and product distributions on the prepared Fe-group NA catalysts in the EG electrooxidation were investigated by cyclic voltammetry and chronoamperometry, and compared with those of the previously reported FeCoNi/C, which clarified the contributory factors of the metal components for the EG electrooxidation activity, C2 product selectivity, and catalyst durability. The Co-containing catalysts, such as Co/C, FeCo/C, and FeCoNi/C, exhibit relatively high catalytic activities for EG electrooxidation, whereas the catalytic performances of Ni-containing catalysts are relatively low. However, we found that the inclusion of Ni is a requisite for the prevention of rapid degradation due to surface modification of the catalyst. Notably, FeCoNi/C shows the highest selectivity for oxalic acid production without CO2 generation at 0.4 V vs. the reversible hydrogen electrode (RHE), resulting from the synergetic contribution of all of the component elements. Finally, we performed power generation using the direct EG alkaline fuel cell in the presence of the Fe-group catalysts. The power density obtained on each catalyst directly reflected the catalytic performances elucidated in the electrochemical experiments for the corresponding catalyst. The catalytic roles and alloying effects disclosed herein provide information on the design of highly efficient electrocatalysts containing Fe-group metals. PMID:25848911

  5. 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

  6. 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

  7. 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.

  8. 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

  9. 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

  10. Endoscopic and Histologic Findings in a Cohort of Uric Acid and Calcium Oxalate Stone Formers

    PubMed Central

    Viers, BR; Lieske, JC; Vrtiska, TJ; Herrera Hernandez, LP; Vaughan, LE; Mehta, RA; Bergstralh, EJ; Rule, AD; Holmes, DR; Krambeck, AE

    2015-01-01

    Objectives To characterize the endoscopic and histologic renal papillary lesions in a cohort of uric acid (UA) stone formers (SF). Methods Data was prospectively obtained during percutaneous nephrolithotomy between 2009–2013. Renal papillae were endoscopically analyzed to quantitate surface area (SA) occupied by plaque or plug, and biopsies were obtained. UA SF were compared to non-SF controls and patients with >50% CaOx in the absence of UA. Results There were 23 UA SF; of which 19 stones (83%) were admixed with CaOx and 4 (17%) were pure. Compared to CaOx SF and controls, UA SF had a higher prevalence of diabetes and obesity, greater serum creatinine and UA, lower eGFR and urine pH, and elevated UA supersaturation. Characteristics of UA SF were compared to 95 CaOx SF, and 19 controls. Overall, 23 (100%) UA SF had endoscopic plaque and 13 (57%) plugs. Endoscopically, UA SF displayed a greater incidence of plugging (57% vs 45% vs 11%; p=0.006) relative to CaOx SF and controls. Likewise, UA SF had a greater %SA of plugging (0.1 vs 0.0; p=0.002) and plaque (2.0 vs 0.9, p=0.006) than controls; but similar amounts to CaOx SF. Histologic plugs were similar in UA and CaOx SF, although CaOx SF demonstrated greater interstitial inflammation on endoscopic biopsy. Conclusions UA and CaOx SF have similar amounts of plaque, while UA SF have more endoscopic but not histological collecting duct plugs. These data suggest overlap between the pathogenesis of UA and CaOx stones. The anchoring site for UA stones remains uncertain. PMID:25681832

  11. 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.

  12. 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.

  13. Recognition of oxalate by a copper(II) polyaza macrobicyclic complex.

    PubMed

    Mateus, Pedro; Delgado, Rita; Brandão, Paula; Félix, Vítor

    2011-06-14

    A new polyamine macrobicyclic compound was synthesised through a [1+1] "tripod-tripod coupling" strategy and using a Schiff base condensation reaction, followed by sodium borohydride reduction. The resulting compound is a heteroditopic cage (btpN(7)) in which one of the head units is appropriate for the coordination of copper(II), whereas the other head is available for additional hydrogen-bonding and electrostatic interactions with substrates. The acid-base behaviour of the new compound, the stability constants of its complex with the Cu(2+) ion and the association constants of the copper(II) cryptate with oxalate (oxa(2-)), malonate (mal(2-)), succinate (suc(2-)), maleate (male(2-)) and fumarate (fum(2-)) were determined by potentiometry at 298.2 K in aqueous solution and at an ionic strength of 0.10 mol dm(-3) in KNO(3). These studies revealed a clear preference of the receptor [CuH(h)btpN(7)H(2)O]((2+h)+) for oxa(2-) over the other dicarboxylate substrates. This arises from co-operativity between metal-anion coordination and electrostatic and hydrogen-bonding interactions, in accordance with the ideal size of this dicarboxylate, which allow it to take full advantage of the potential binding sites of the receptor. A qualitative indicator-displacement study, in agreement with the potentiometric studies, demonstrated that the copper cryptate receptor can be used as a selective visual sensor for oxalate. PMID:21557358

  14. 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

  15. Biogenesis of Oxalate in Plant Tissues

    PubMed Central

    Chang, Chi-Cheng; Beevers, Harry

    1968-01-01

    Red beet root discs aerated in potassium phosphate for 2 to 3 days and young spinach leaves actively produce oxalate. A series of labeled compounds was supplied to each of these tissues to determine the extent of conversion to oxalate. Similar results were obtained with the 2 tissues except that in the leaf tissue glyoxylate and glycolate were outstandingly good precursors. Carbon from glucose, acetate, and particularly from some acids of the tricarboxylic acid cycle was recovered in oxalate. Extracts from both tissues were found to contain an enzyme which converts oxaloacetate to oxalate and acetate. The enzyme was partially purified and some of its properties are described. A pathway of oxalate synthesis which does not include glycolate or its oxidase is therefore proposed. PMID:16656975

  16. Multi-element analysis of milk by ICP-oa-TOF-MS after precipitation of calcium and proteins by oxalic and nitric acid.

    PubMed

    Husáková, Lenka; Urbanová, Iva; Šrámková, Jitka; Konečná, Michaela; Bohuslavová, Jana

    2013-03-15

    In this work a simple technique employing oxalic and nitric acid to cow's milk samples prior to analysis by inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometry (ICP-oa-TOF-MS) was introduced. After the precipitation of calcium and proteins via oxalic and nitric acid, respectively, the resulting liquid phase was aspirated with a concentric glass nebulizer for ICP-TOF-MS determination of trace elements. Precipitation of proteins is essential for better separation of solid and liquid phase of modified samples. Separation of calcium as a precipitated non-soluble oxalate enables the elimination of spectral interferences originating from different calcium containing species like (40)Ca(35)Cl(+), (40)Ca(37)Cl(+), (43)Ca(16)O(+), (40)Ca(18)O(+), (44)Ca(16)O(+), (43)Ca(16)O(1)H(+) onto the determination of As, Se, Co and Ni whose assay is more difficult when using conventional quadrupole instruments. High detection capability is further an advantage as the approach enables the analysis without dilution. The methodology may serve, in addition, for a fast and sensitive determination of some other elements. After that, direct, reliable and simultaneous determination of 16 elements (Li, Be, B, V, Cr, Mn, Ni, Co, Ga, As, Se, Mo, Sn, Sb, Cs, Tl) at trace and ultra-trace levels in milk can be performed under optimum instrumental conditions and by using Rh as an internal standard. Accuracy and precision was assessed by measuring NCS ZC73015 milk powder control standard, yielding results in agreement with certified values and RSD <10%. The accuracy was also checked by comparison of the results of the proposed method with those found by a method based on a microwave-assisted digestion of real samples. PMID:23598096

  17. Secondary porosity revisited: The chemistry of feldspar dissolution by carboxylic acids and anions

    SciTech Connect

    Stoessell, R.K. ); Pittman, E.D. )

    1990-12-01

    Carboxylic acids in subsurface waters have been proposed as agents for dissolving feldspars and complexing aluminum to create secondary porosity in sandstones. Previously published experimental work indicated high aluminum mobility in the presence of carboxylic acid solutions. In order to further evaluate aluminum mobility, alkali feldspar dissolution experiments were run at 100C and 300 bars in the presence of mono- and dicarboxylic acids and their anions. Experimental results imply that under reservoir conditions, aluminum-organic anion complexes are insignificant for acetate and propionate and possibly significant for oxalate and malonate. Propionate appeared to inhibit alkali feldspar dissolution and, hence, may retard aluminum mobility. Dissolution of feldspar in the presence of oxalic and acetic acid can be explained by enhanced dissolution kinetics and greater aluminum mobility under low-pH conditions. The general absence of such low-pH fluids in subsurface reservoirs makes this an unlikely mechanism for creating secondary porosity. Also, the thermal instability of oxalate and malonate limits their aluminum-complexing potential in reservoirs at temperatures above 100C.

  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. Reuse of sewage sludge as a catalyst in ozonation--efficiency for the removal of oxalic acid and the control of bromate formation.

    PubMed

    Wen, Gang; Pan, Zhi-Hui; Ma, Jun; Liu, Zheng-Qian; Zhao, Lei; Li, Jun-Jing

    2012-11-15

    Sewage derived sludge is produced with an annual amount increase of 2% all over the world and it is an urgent issue to be addressed by human being. In the present study, sludge was converted into sludge-based catalyst (SBC) with ZnCl2 as activation agent and characterized by several methods (e.g., scanning electron microscope, X-ray photoelectron spectroscope and Fourier transform infrared spectroscope). Then it was used as a catalyst to enhance the removal of refractory organic matter, oxalic acid, and to control the formation of bromate (BrO3-) in bench semi-continuous ozonation experiments. The effects of various operating parameters on the control of BrO3- formation were investigated. Furthermore, the mechanism for the enhancement of organic matter removal and the control of BrO3- formation was discussed as well. Results indicate that the combination of SBC with ozone shows a strong synergistic effect, resulting in a notable improvement on oxalic acid removal. A crucial surface reaction mechanism for the enhancement of organic matter removal is proposed on the basis of negative effect of higher pH and no inhibition effect of tert-butanol. The control for BrO3- formation was demonstrated and the reason for its control in the process of O3/SBC is the combined effect of SBC reductive properties, ozone exposure decrease and hydrogen peroxide concentration increase. PMID:23021317

  20. 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

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. Selective dissolution of magnetic iron oxides in the acid-ammonium oxalate/ferrous iron extraction method-I. Synthetic samples

    NASA Astrophysics Data System (ADS)

    van Oorschot, Ingeborg H. M.; Dekkers, Mark J.

    2001-06-01

    In soil magnetism, the magnetic parameters alone are not always sufficient to distinguish the lithogenic from the pedogenic magnetic fractions. Sequential extraction techniques have therefore been incorporated into magnetic studies to constrain the environmental interpretation. Here we report on the dissolution behaviour of magnetite and maghemite in the acid-ammonium oxalate method to see whether the method is suitable for specific dissolution of magnetic minerals from soils and sediments. To prevent changes in the extraction mechanism during the experiments (see Appendix A), we used an adapted version of the acid-ammonium oxalate (AAO) method, in which Fe2+ is added to the extraction solution prior to the experiment [the AAO-Fe(II) method]. The procedure was divided into several 30min extraction steps to check the dissolution progress. Synthetic samples containing a quartz matrix with 0.1wt per cent of iron oxides were extracted with the AAO-Fe(II) method. The iron oxides consisted of either magnetite or maghemite with grain sizes of <0.5µm (fine grained or SD/PSD) and <5µm (coarse grained or MD/PSD), or a 1:1 mixture of both minerals. Because only magnetite and maghemite were studied, the changes in magnetic characteristics could be monitored after each extraction step by analysis of the bulk susceptibility and hysteresis parameters measured at room temperature. The AAO-Fe(II) method preferentially dissolved the smaller iron oxides from the samples. For samples containing iron oxides with coarse grain size there is a preference for dissolving maghemite rather than magnetite. Extractions of the samples containing mixtures of two different grain sizes or with different mineralogy show that the method preferentially dissolves the smaller grains before attacking the coarse grains in the sample.

  8. 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.

  9. 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

  10. 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. PMID:25662688

  11. 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

  12. Organic acids as cloud condensation nuclei: Laboratory studies of highly soluble and insoluble species

    NASA Astrophysics Data System (ADS)

    Pradeep Kumar, P.; Broekhuizen, K.; Abbatt, J. P. D.

    2003-05-01

    The ability of sub-micron-sized organic acid particles to act as cloud condensation nuclei (CCN) has been examined at room temperature using a newly constructed continuous-flow, thermal-gradient diffusion chamber (TGDC). The organic acids studied were: oxalic, malonic, glutaric, oleic and stearic. The CCN properties of the highly soluble acids - oxalic, malonic and glutaric - match very closely Köhler theory predictions which assume full dissolution of the dry particle and a surface tension of the growing droplet equal to that of water. In particular, for supersaturations between 0.3 and 0.6, agreement between the dry particle diameter which gives 50% activation and that calculated from Köhler theory is to within 3nm on average. In the course of the experiments, considerable instability of glutaric acid particles was observed as a function of time and there is evidence that they fragment to some degree to smaller particles. Stearic acid and oleic acid, which are both highly insoluble in water, did not activate at supersaturations of 0.6% with dry diameters up to 140nm. Finally, to validate the performance of the TGDC, we present results for the activation of ammonium sulfate particles that demonstrate good agreement with Köhler theory if solution non-ideality is considered. Our findings support earlier studies in the literature that showed highly soluble organics to be CCN active but insoluble species to be largely inactive.

  13. 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

  14. 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.

  15. 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...

  16. Anaerobic Oxalate Degradation: Widespread Natural Occurrence in Aquatic Sediments

    PubMed Central

    Smith, Richard L.; Oremland, Ronald S.

    1983-01-01

    Significant concentrations of oxalate (dissolved plus particulate) were present in sediments taken from a diversity of aquatic environments, ranging from 0.1 to 0.7 mmol/liter of sediment. These included pelagic and littoral sediments from two freshwater lakes (Searsville Lake, Calif., and Lake Tahoe, Calif.), a hypersaline, meromictic, alkaline lake (Big Soda Lake, Nev.), and a South San Francisco Bay mud flat and salt marsh. The oxalate concentration of several plant species which are potential detrital inputs to these aquatic sediments ranged from 0.1 to 5.0% (wt/wt). In experiments with litter bags, the oxalate content of Myriophyllum sp. samples buried in freshwater littoral sediments decreased to 7% of the original value in 175 days. This suggests that plant detritus is a potential source of the oxalate within these sediments. [14C]oxalic acid was anaerobically degraded to 14CO2 in all sediment types tested, with higher rates evident in littoral sediments than in the pelagic sediments of the lakes studied. The turnover time of the added [14C]oxalate was less than 1 day in Searsville Lake littoral sediments. The total sediment oxalate concentration did not vary significantly between littoral and pelagic sediments and therefore did not appear to be controlling the rate of oxalate degradation. However, depth profiles of [14C]oxalate mineralization and dissolved oxalate concentration were closely correlated in freshwater littoral sediments; both were greatest in the surface sediments (0 to 5 cm) and decreased with depth. The dissolved oxalate concentration (9.1 μmol/liter of sediment) was only 3% of the total extractable oxalate (277 μmol/liter of sediment) at the sediment surface. These results suggest that anaerobic oxalate degradation is a widespread phenomenon in aquatic sediments and may be limited by the dissolved oxalate concentration within these sediments. PMID:16346332

  17. 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...

  18. Seasonal and spatial variability of the OM/OC mass ratios and high regional correlation between oxalic acid and zinc in Chinese urban organic aerosols

    NASA Astrophysics Data System (ADS)

    Xing, L.; Fu, T.-M.; Cao, J. J.; Lee, S. C.; Wang, G. H.; Ho, K. F.; Cheng, M.-C.; You, C.-F.; Wang, T. J.

    2013-04-01

    We calculated the organic matter to organic carbon mass ratios (OM/OC mass ratios) in PM2.5 collected from 14 Chinese cities during summer and winter of 2003 and analyzed the causes for their seasonal and spatial variability. The OM/OC mass ratios were calculated two ways. Using a mass balance method, the calculated OM/OC mass ratios averaged 1.92 ± 0.39 year-round, with no significant seasonal or spatial variation. The second calculation was based on chemical species analyses of the organic compounds extracted from the PM2.5 samples using dichloromethane/methanol and water. The calculated OM/OC mass ratio in summer was relatively high (1.75 ± 0.13) and spatially-invariant due to vigorous photochemistry and secondary organic aerosol (OA) production throughout the country. The calculated OM/OC mass ratio in winter (1.59 ± 0.18) was significantly lower than that in summer, with lower values in northern cities (1.51 ± 0.07) than in southern cities (1.65 ± 0.15). This likely reflects the wider usage of coal for heating purposes in northern China in winter, in contrast to the larger contributions from biofuel and biomass burning in southern China in winter. On average, organic matter constituted 36% and 34% of Chinese urban PM2.5 mass in summer and winter, respectively. We report, for the first time, a high regional correlation between Zn and oxalic acid in Chinese urban aerosols in summer. This is consistent with the formation of stable Zn oxalate complex in the aerosol phase previously proposed by Furukawa and Takahashi (2011). We found that many other dicarboxylic acids were also highly correlated with Zn in the summer Chinese urban aerosol samples, suggesting that they may also form stable organic complexes with Zn. Such formation may have profound implications for the atmospheric abundance and hygroscopic properties of aerosol dicarboxylic acids.

  19. Chemoselective Intramolecular Carbonyl Ylide Formation through Electronically Differentiated Malonate Diesters.

    PubMed

    Nakhla, Mina C; Lee, Che-Wah; Wood, John L

    2015-12-01

    A method for chemoselective carbonyl ylide formation utilizing the Rh(II) catalyzed decomposition of electronically differentiated diazo malonates is disclosed. Treatment of ethyl, trifluoro ethyl diazo malonate with a Rh(II) catalyst selectively forms a carbonyl ylide from the relatively electron rich ethyl ester. This carbonyl ylide can be trapped by various alkynes giving highly functionalized oxabicyclic compounds in a chemo-, regio-, and diastereoselective fashion. PMID:26584509

  20. 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

  1. 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.

  2. 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

  3. Oxalate in grain amaranth.

    PubMed

    Gélinas, Bruce; Seguin, Philippe

    2007-06-13

    Grain amaranth (Amaranthus spp.) is a widely adaptable C4 pseudo-cereal crop that has interesting nutritional characteristics including high protein and calcium concentrations and a lack of gluten. To date, no antinutrient has been found at problematic levels in grain amaranth; however, oxalate has not been thoroughly studied. Dietary oxalate is a potential risk factor for kidney stone development, and its presence in food lowers calcium and magnesium availability. Oxalate concentration and forms and calcium and magnesium concentrations were determined in 30 field-grown grain amaranth genotypes from the species A. cruentus, A. hybrid, and A. hypochondriacus. The effects of seeding date and fertilization with calcium ammonium nitrate were evaluated in field experiments conducted in multiple environments; the effects of cooking were also evaluated. Mean total oxalate concentration in the 30 genotypes analyzed was 229 mg/100 g, with values ranging between 178 and 278 mg/100 g, the greatest proportion being insoluble (average of 80%). Calcium concentration averaged 186 mg/100 g and ranged between 134 and 370 mg/100 g, whereas magnesium averaged 280 mg/100 g and ranged between 230 and 387 mg/100 g. Fertilization only marginally increased total oxalate concentration and had no effects on other variables. Seeding date had no effects on any of the variables studied. Boiling increased the proportion of soluble oxalate but did not affect total oxalate concentration. Grain amaranth can be considered a high oxalate source, however, as most is in insoluble form, and due to its high calcium and magnesium concentrations, oxalate absorbability could be low. This should be confirmed by bioavailability studies. PMID:17511467

  4. 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.

  5. 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

  6. 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

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

    PubMed

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

    2016-02-01

    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. PMID:26771075

  8. 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.

  9. CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

    PubMed Central

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

    2014-01-01

    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. PMID:25004118

  10. 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.

  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. 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

  13. 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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  15. 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.

  16. 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

  17. The effects of oxalate treatment on the smear layer of ground surfaces of human dentine.

    PubMed

    Pashley, D H; Galloway, S E

    1985-01-01

    The layer was evaluated by scanning electron microscopy and by measurement of hydraulic conductance before and after 2-min topical treatment with potassium chloride, neutral potassium oxalate, half-neutralized oxalic acid or both neutral and acidic oxalates. The treated smear layers were then re-evaluated microscopically and functionally both before and after acid challenge. The layers treated with KCl were not altered either microscopically or functionally and were susceptible to acid etching. Dentine surfaces treated with either oxalate solutions became less permeable and were acid-resistant. PMID:3866520

  18. 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

  19. 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

  20. 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

  1. 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.

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

    PubMed

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

    2013-07-01

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

  3. 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

  4. An electrochemiluminescent biosensor for uric acid based on the electrochemiluminescence of bis-[3,4,6-trichloro-2-(pentyloxycarbonyl)-phenyl] oxalate on an ITO electrode modified by an electropolymerized nickel phthalocyanine film.

    PubMed

    Lin, Zhenyu; Chen, Zhihuang; Liu, Yan; Wang, Jian; Chen, Guonan

    2008-06-01

    Nickel(ii) tetrasulfophthalo-cyanine (NiTSPc) could be electrodeposited onto an indium tin oxide (ITO) electrode to form an electropolymerization film of NiTSPc. The electrochemiluminescent (ECL) behavior of bis-[3,4,6-trichloro-2-(pentyloxy-carbonyl)-phenyl] oxalate (BTPPO) on this modified electrode was investigated in detail. The emission of ECL of BTPPO can be greatly enhanced by hydrogen peroxide at this modified electrode. Thus, a new ECL biosensor for uric acid was developed based on the enzymatic reaction of uric acid in the presence of uricase to produce H(2)O(2). The developed sensor has been used to detect uric acid in real serum samples, and the results compared well with those obtained by the routine method. PMID:18493682

  5. 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.

  6. Mimicking the growth of a pathologic biomineral: shape development and structures of calcium oxalate dihydrate in the presence of polyacrylic acid.

    PubMed

    Thomas, Annu; Rosseeva, Elena; Hochrein, Oliver; Carrillo-Cabrera, Wilder; Simon, Paul; Duchstein, Patrick; Zahn, Dirk; Kniep, Rüdiger

    2012-03-26

    The morphogenesis of calcium oxalate hydrates in aqueous solutions was investigated by varying the pH, oxalate concentration, and the concentration of the sodium salt of polyacrylate (PAA). With increasing amounts of PAA in solution, the shape of tetragonal calcium oxalate dihydrate (COD) changes from bipyramidal through elongated bipyramidal prisms to dumbbells and finally reverts to rodlike tetragonal bipyramidal prisms. PAA is incorporated into the prismatic zones of the growing COD crystals, thereby reducing the growth rate of the {100} faces along the <100> direction. Dumbbells start to develop through "non-crystallographic" branching from the prism faces and the formation of "multiple head" crystals. Adsorption of PAA on the rough surfaces of the splitting individuals supports the selection of new subindividuals and leads to the formation of core-shell patterns. The various shapes and structures of the biomimetic COD/PAA crystals and aggregates are closely related to the well-known "pathologic" individuals observed in the urine of patients with urinary disease (including urinary stones). PMID:22354632

  7. Regulation and Evolution of Malonate and Propionate Catabolism in Proteobacteria

    PubMed Central

    Suvorova, I. A.; Ravcheev, D. A.

    2012-01-01

    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. PMID:22505679

  8. 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.

  9. 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.

  10. 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 utilizing ascorbic acid as the precursor in oxalate biosynthesis. In this study, we address the possibility that more than one pathway of oxalate biosynthesis and calcium oxalate formation occurs in Medicago truncatula. Like wildtype, developing leaves of...

  11. 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...

  12. Postprandial hyperoxaluria and intestinal oxalate absorption in idiopathic renal stone disease

    SciTech Connect

    Schwille, P.O.; Hanisch, E.; Scholz, D.

    1984-10-01

    Calcium and oxalate were studied in daily, fasting and postprandial urine specimens from healthy subjects and patients with idiopathic renal calcium stones in response to a test meal free of oxalate, and supplemented with calcium and 14carbon-oxalic acid. The data showed that the amount of oxalate in fasting urine of patients with stones did not differ from that in controls. Generally, patients with stones had considerable postprandial hyperoxaluria in terms of excretion and concentration, associated with a significantly higher degree of supersaturation with regard to calcium oxalate compared to controls. These findings were paralleled by decreased intestinal absorption of 14carbon-oxalate and by unchanged 24-hour urinary oxalate. Although the source of increased p

  13. 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

  14. 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.

  15. Abortiporus biennis tolerance to insoluble metal oxides: oxalate secretion, oxalate oxidase activity, and mycelial morphology.

    PubMed

    Graz, Marcin; Jarosz-Wilkołazka, Anna; Pawlikowska-Pawlega, Bozena

    2009-06-01

    The ability of Abortiporus biennis to tolerate and solubilize toxic metal oxides (Cu(2)O, Al(2)O(3), ZnO, CuFe(2)O(4)Zn, CdO, and MnO(2)) incorporated into agar media was investigated and the growth rate, oxalic acid secretion, and mycelial morphology were monitored. Among the tested metal oxides, formation of clear zones underneath the mycelium growing on Cu(2)O- and ZnO-amended plates was observed. ZnO, CdO and Cu(2)O caused the highest rate of fungal growth inhibition. An increased level of oxalic acid concentration was detected as a response of A. biennis to the presence of Cu(2)O, MnO(2), ZnO and CuFe(2)O(4)Zn in growth medium. The oxalate oxidase (OXO) was found to be responsible for oxalic acid degradation in A. biennis cultivated in metal-amended media. An increased level of OXO was observed in media amended with Cu(2)O, ZnO and MnO(2). Confocal microscopy used in this study revealed changes in mycelial morphology which appeared as increased hyphal branching, increased septation and increased spore number. PMID:18985279

  16. 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.

  17. The effects of oxalate-containing products on the exposed dentine surface: an SEM investigation.

    PubMed

    Gillam, D G; Mordan, N J; Sinodinou, A D; Tang, J Y; Knowles, J C; Gibson, I R

    2001-11-01

    In-office products containing oxalates have been claimed to be clinically effective in reducing dentine sensitivity, although there has been limited supporting clinical data. The rationale for their use appears to be based on their potential to act as occluding and/or nerve desensitizing agents. Four commercially available oxalate-containing products were applied to etched dentine discs and the extent of tubule occlusion was observed by scanning electron microscopy. Tenure Quick (aluminium oxalate), Sensodyne Sealant (ferric oxalate) and MS Coat (oxalic acid) covered the dentine surface and occluded the tubules. However, Butler Protect (potassium oxalate) did not cover the surface to any great extent but provided some occlusion. The presence of oxalates after application to glass slides and dentine discs was examined using thin film X-ray diffraction. From samples on glass, only potassium oxalate could be clearly identified (JCPDS 14-0845). No oxalate was detected on dentine discs in either thin film geometry or standard theta two theta mode. We have demonstrated that professionally applied in-office products containing oxalate are capable of covering the dentine surface and/or occluding the tubules to varying degrees. However, X-ray diffraction analysis was unable to confirm the oxalate profile for all products as described in the available commercial literature. PMID:11722720

  18. 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.

  19. Effect of dietary oxalate and calcium on urinary oxalate and risk of formation of calcium oxalate kidney stones.

    PubMed

    Massey, L K; Roman-Smith, H; Sutton, R A

    1993-08-01

    Dietary restriction of oxalate intake has been used as therapy to reduce the risk of recurrence of calcium oxalate kidney stones. Although urinary oxalate is derived predominantly from endogenous synthesis, it may also be affected by dietary intake of oxalate and calcium. The risk of increasing urinary oxalate excretion by excessive consumption of dietary oxalate is greatest in individuals with a high rate of oxalate absorption, both with and without overt intestinal disease. Although oxalate-rich foods enhanced excretion of urinary oxalate in normal volunteers, the increase was not proportional to the oxalate content of the food. Only eight foods--spinach, rhubarb, beets, nuts, chocolate, tea, wheat bran, and strawberries--caused a significant increase in urinary oxalate excretion. Restriction of dietary calcium enhances oxalate absorption and excretion, whereas an increase in calcium intake may reduce urinary oxalate excretion by binding more oxalate in the gut. This review of the literature indicates that initial dietary therapy for stone-forming individuals can be limited to the restriction of foods definitely shown to increase urinary oxalate. The effects of oxalate-restricted diets on urinary oxalate should be evaluated by means of laboratory analyses of urine composition. Subsequent long-term therapy can be recommended if beneficial results are obtained from oxalate restriction at an appropriate calcium intake. PMID:8335871

  20. Enhanced concentrations of citric acid in spring aerosols collected at the Gosan background site in East Asia

    NASA Astrophysics Data System (ADS)

    Jung, Jinsang; Kawamura, Kimitaka

    2011-09-01

    In order to investigate water-soluble dicarboxylic acids and related compounds in the aerosol samples under the Asian continent outflow, total suspended particle (TSP) samples ( n = 32) were collected at the Gosan site in Jeju Island over 2-5 days integration during 23 March-1 June 2007 and 16-24 April 2008. The samples were analyzed for water-soluble dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls using a capillary gas chromatography technique. We found elevated concentrations of atmospheric citric acid (range: 20-320 ng m -3) in the TSP samples during mid- to late April of 2007 and 2008. To specify the sources of citric acid, dicarboxylic acids and related compounds were measured in the pollen sample collected at the Gosan site (Pollen_Gosan), authentic pollen samples from Japanese cedar ( Cryptomeria) (Pollen_cedar) and Japanese cypress ( Chamaecyparis obtusa) (Pollen_cypress), and tangerine fruit produced from Jeju Island. Citric acid (2790 ng in unit mg of pollen mass) was found as most abundant species in the Pollen_Gosan, followed by oxalic acid (2390 ng mg -1). Although citric acid was not detected in the Pollen_cedar and Pollen_cypress as major species, it was found as a dominant species in the tangerine juice while malic acid was detected as major species in the tangerine peel, followed by oxalic and citric acids. Since Japanese cedar trees are planted around tangerine farms to prevent strong winds from the Pacific Ocean, citric acid that may be directly emitted from tangerine is likely adsorbed on pollens emitted from Japanese cedar and then transported to the Gosan site. Much lower malic/citric acid ratios obtained under cloudy condition than clear condition suggest that malic acid may rapidly decompose to lower molecular weight compounds such as oxalic and malonic acids (

  1. Identification of calcium oxalate crystals using alizarin red S stain.

    PubMed

    Proia, A D; Brinn, N T

    1985-02-01

    Calcium oxalate crystals stain with alizarin red S at a pH of 7.0 but not at a pH of 4.2. In contrast, calcium phosphate and calcium carbonate stain at a pH of both 7.0 and 4.2. This difference allows presumptive identification of calcium oxalate deposits. The identity of calcium oxalate can then be confirmed by its insolubility in 2M acetic acid, since both calcium carbonate and calcium phosphate are soluble. We have applied this procedure for several years and have found it to be a rapid, reliable, and technically simple procedure for distinguishing calcium oxalate from other calcium deposits. PMID:2579619

  2. 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.

  3. Heterogeneous photodegradation of pentachlorophenol with maghemite and oxalate under UV illumination.

    PubMed

    Lan, Qing; Li, Fangbai; Liu, Chengshuai; Li, Xiang-Zhong

    2008-11-01

    The degradation of pentachlorophenol (PCP) in a heterogeneous system with maghemite (gamma-Fe2O3) and oxalate under UV illumination was investigated in this study. The results of adsorption experiments demonstrated competitive adsorption between PCP and oxalic acid on the surface of gamma-Fe2O3. The results of photodegradation experiments showed that the rate of PCP degradation strongly relied on the oxalic acid concentration and that an optimal tested initial concentration of oxalic acid (Cox(0)) of 0.8 mM was obtained under our experimental conditions. It was observed that a sufficient amount of oxalic acid can be adsorbed on the gamma-Fe2O3 to form various Fe(III)-oxalate complexes at Cox(o) = 0.8 mM. During the photoreaction, Fe(C2O4)2- and Fe(C2O4)3(3-) were found to be the dominant Fe(III)-oxalate complexes at different Cox(0), while Fe(C2O4)2(2-) was the dominant Fe(II)-oxalate complex at Cox(0) > or = 0.8 mM. The mechanism of H2O2 formation and consumption in the UV-irradiated gamma-Fe2O3/oxalate system was proposed and evaluated. Furthermore, six intermediates of PCP degradation were identified by GC/MS, HPLC, and IC analyses, respectively, and a possible pathway of PCP degradation in such a system was proposed. PMID:19031881

  4. Putative Aspergillus niger-induced oxalate nephrosis in sheep.

    PubMed

    Botha, C J; Truter, M; Bredell, T; Lange, L; Mülders, M S G

    2009-03-01

    A sheep farmer provided a maize-based brewer's grain (mieliemaroek) and bales of Eragrostis curvula hay to ewes and their lambs, kept on zero-grazing in pens. The 'mieliemaroek' was visibly mouldy. After 14 days in the feedlot, clinical signs, including generalised weakness, ataxia of the hind limbs, tremors and recumbency, were noticed. Six ewes died within a period of 7 days. A post mortem examination was performed on 1 ewe. The carcass appeared to be cachectic with mild effusions into the body cavities; mild lung congestion and pallor of the kidneys were observed. Microscopical evaluation revealed nephrosis and birefringent oxalate crystals in the renal tubules when viewed under polarised light. A provisional diagnosis of oxalate nephrosis with subsequent kidney failure was made. Amongst other fungi, Aspergillus niger was isolated from 'mieliemaroek' samples submitted for fungal culture and identification. As A. niger is known to synthesise oxalates, a qualitative screen to detect oxalic acid in the mieliemaroek and purified A. niger isolates was performed using high-performance liquid chromatography (HPLC). Oxalic acid was detected, which supported a diagnosis of soluble oxalate-induced nephropathy. PMID:19653520

  5. 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...

  6. Seasonal and spatial variability of the organic matter-to-organic carbon mass ratios in Chinese urban organic aerosols and a first report of high correlations between aerosol oxalic acid and zinc

    NASA Astrophysics Data System (ADS)

    Xing, L.; Fu, T.-M.; Cao, J. J.; Lee, S. C.; Wang, G. H.; Ho, K. F.; Cheng, M.-C.; You, C.-F.; Wang, T. J.

    2013-01-01

    We calculated the organic matter to organic carbon mass ratios (OM/OC mass ratios) in PM2.5 collected from 14 Chinese cities during summer and winter of 2003 and analyzed the causes for their seasonal and spatial variability. The OM/OC mass ratios were calculated two ways. Using a mass balance method, the calculated OM/OC mass ratios averaged 1.92 ± 0.39 yr-round, with no significant seasonal or spatial variation. The second calculation was based on chemical species analyses of the organic compounds extracted from the PM2.5 samples using dichloromethane/methanol and water. The calculated OM/OC mass ratio in summer was relatively high (1.75 ± 0.13) and spatially-invariant, due to vigorous photochemistry and secondary OA production throughout the country. The calculated OM/OC mass ratio in winter (1.59 ± 0.18) was significantly lower than that in summer, with lower values in northern cities (1.51 ± 0.07) than in southern cities (1.65 ± 0.15). This likely reflects the wider usage of coal for heating purposes in northern China in winter, in contrast to the larger contributions from biofuel and biomass burning in southern China in winter. On average, organic matters constituted 36% and 34% of Chinese urban PM2.5 mass in summer and winter, respectively. We reported, for the first time, high correlations between Zn and oxalic acid in Chinese urban aerosols in summer. This is consistent with the formation of stable Zn oxalate complex in the aerosol phase previously proposed by Furukawa and Takahashi (2011). We found that many other dicarboxylic acids were also highly correlated with Zn in the summer Chinese urban aerosol samples, suggesting that they may also form stable organic complexes with Zn. Such formation may have profound implications for the atmospheric abundance and hygroscopic property of aerosol dicarboxylic acids.

  7. 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

  8. Choice between autotrophy and heterotrophy in Pseudomonas oxalaticus. Utilization of oxalate by cells after adaptation from growth on formate to growth on oxalate

    PubMed Central

    Blackmore, Maureen A.; Quayle, J. R.; Walker, I. O.

    1968-01-01

    1. The labelling patterns of phosphoglycerate obtained from formate-grown or oxalate-grown Pseudomonas oxalaticus after exposure for 15sec. to [14C]formate or [14C]oxalate respectively were determined. 2. The phosphoglycerate obtained from the formate-grown cells contained 78% of the radioactivity in the carboxyl group. This is in accord with that predicted for operation of the ribulose diphosphate cycle of carbon dioxide fixation. 3. The labelling pattern of the phosphoglycerate obtained from the oxalate-grown cells approached uniformity, as predicted for the heterotrophic pathway of oxalate assimilation. The departure from complete uniformity may have been due to concurrent 14CO2 fixation into C4 dicarboxylic acids. 4. The labelling pattern of phosphoglycerate obtained from cells that had just started to grow on oxalate after adaptation from formate was determined after incubation of the cells for 15sec. with [14C]oxalate. This pattern approached uniformity. 5. The pathway of incorporation of 14CO2 into cells that had just started to grow on oxalate after adaptation from formate, in the presence of either formate or oxalate as energy source, was studied by chromatographic and radio-autographic analysis. 6. It is concluded from the isotopic data that a mixed heterotrophic–autotrophic metabolism, with the former mode predominating, operates in the initial stages of growth on oxalate after adaptation from growth on formate. PMID:16742592

  9. 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

  10. Use of a ruthenium(III), iron(II), and nickel(II) hexacyanometallate-modified graphite electrode with immobilized oxalate oxidase for the determination of urinary oxalate.

    PubMed

    Milardović, S; Grabarić, Z; Rumenjak, V; Blau, N; Milosević, D

    2001-01-01

    This paper describes the performance of a biosensor with an Ru(III), Ni(II), and Fe(II) hexacyanometallate-modified graphite electrode and immobilized oxalate oxidase for the determination of urinary oxalate. The addition of ruthenium enhances the electrochemical reversibility and chemical stability of the electrocrystallized layer and improves the sensitivity of the biosensor. Hydrogen peroxide, produced by the enzyme-catalyzed oxidation of oxalate, was measured at -50 mV vs an Hg Hg2CI2 3M KCl electrode in a solution of pH 3.6 succinic buffer, 0.1 M KCl, and 5.4mM ethylenediaminetetraacetic acid. The linear concentration range for the determination of oxalate was 0.18-280 microM. The recoveries of added oxalate (10-35 microM) from aqueous solution ranged from 99.5 to 101.7%, whereas from urine samples without oxalate (or with a concentration of oxalate below the detection limit) the recoveries of added oxalate ranged from 91.4 to 106.6%. The oxalate in 24 h urine samples, taken during their daily routine from 35 infants and children, was measured and found to range from 0.6 to 121.7 mg/L. There were no interferences from uric acid, acetylsalicylic acid, and urea in the concentration range investigated, but paracetamol and ascorbic acid did interfere. A good correlation (R2 = 0.9242) was found between values obtained for oxalate in real urine samples by 2 laboratories, with the proposed biosensor and ion chromatography, respectively. PMID:11767164

  11. Method to Determine Oxalate in High-Level Sludge by Ion Chromatography

    SciTech Connect

    Coleman, C.J.

    2002-12-19

    The Sludge Batch 3 macrobatch feed to the DWPF is expected to contain a relatively high concentration of oxalate. A simple acid addition at room temperature has been shown to be in high-level sludge. This sample preparation requires only about five minutes and yields solutions suitable for oxalate determinations by ion chromatography.

  12. 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...

  13. ADVANCES IN OUR UNDERSTANDING OF CALCIUM OXALATE CRYSTAL FORMATION AND FUNCTION IN PLANTS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Calcium oxalate crystal formation in plants appears to play a central role in a variety of important functions, including tissue calcium regulation, protection from herbivory, and metal detoxification. Evidence is mounting to support ascorbic acid as the primary precursor to oxalate biosynthesis. ...

  14. 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

  15. 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.

  16. 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.

  17. 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

  18. Oxalate desensitising treatment of dentinal surface.

    PubMed

    Mongiorgi, R; Prati, C; Toschi, E; Riva di Sanseverino, L

    1991-04-01

    It is well known that a typical painful feeling is caused by impact of different agents and by thermodynamic conditions upon the dentine layer of the tooth. Therefore the action by artificial solutions should be tested to study how the induced modifications might inhibit the pain. The aim of the present study is to evaluate by scanning electron microscopy (SEM) the morphology of dentine surface after different chemical treatments. Oxalate solutions are able to produce a layer of large crystals, while acid solutions remove the smear layer and open the dentinal tubules. PMID:1910743

  19. Stable carbon isotopic composition of low-molecular-weight dicarboxylic acids and ketoacids in remote marine aerosols

    NASA Astrophysics Data System (ADS)

    Wang, Haobo; Kawamura, Kimitaka

    2006-04-01

    We determined stable carbon isotopic composition (δ13C) of C2 to C9 dicarboxylic acids (DCAs) and some ketoacids in the marine aerosols from the western Pacific and Southern Ocean (35°N to 65°S). On average, oxalic (mean, -16.8‰), adipic (-17.2‰), and glyoxylic (-17.6‰) acids showed heavier δ13C, whereas maleic (-24.2‰), methylmalonic (-23.6‰), and phthalic (-23.1‰) acids were more depleted in 13C. Oxalic acid presented very diverse δ13C values (-27 to -7‰), which increased from midlatitudes toward the equator. A similar latitudinal trend of δ13C was also found for malonic, succinic, and adipic acids. However, such a trend was not observed for phthalic, maleic, and glyoxylic acids. We suggest that the δ13C increase toward the equator is associated with photochemically aged air masses, in which kinetic isotope effects for photochemical degradation of DCAs may be important. Differences in δ13C of some saturated DCAs were also found to increase from midlatitudes to the equator.

  20. 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.

  1. Importance of oxalate precursors for oxalate metabolism in rats.

    PubMed

    Ogawa, Y; Miyazato, T; Hatano, T

    1999-11-01

    Three metabolic precursors of oxalate were compared after intravenous administration to rats by measuring the urinary excretion of oxalate and related substances using capillary electrophoresis. Urine specimens were collected hourly from eight male Wistar rats (approximately 200 g) in each group. Glyoxylate (2 mg), glycolate (10 mg), and hydroxypyruvate (100 mg) were almost equally oxalogenic based on urinary oxalate excretion, with 22.0, 6.1, and 0.4% of the respective doses being converted into oxalate, 3, 8.9, and 0.2% into glycolate, and 1, 0.1, and 0.003% into glyoxylate. The mean urinary excretion of oxalate peaked between 1 and 2 h, while that of glycolate peaked at 1 h. The baseline urinary excretion of glycolate and glyoxylate was 0.11 to 0.24 micromol/h and 0.0 to 8.3 nmol/h, respectively, and all three agents caused a significant increase of urinary glycolate excretion for 2 to 3 h. Only glyoxylate administration increased urinary glyoxylate excretion at 1 h. Hydroxypyruvate administration significantly increased urinary hydroxypyruvate, glycerate, and citrate excretion at 1 to 2 h. The increase of urinary citrate excretion remains to be explained. PMID:10541259

  2. Neuroprotective effects of M826, a reversible caspase-3 inhibitor, in the rat malonate model of Huntington's disease

    PubMed Central

    Toulmond, Sylvie; Tang, Keith; Bureau, Yves; Ashdown, Helen; Degen, Sarah; O'Donnell, Ruth; Tam, John; Han, Yongxin; Colucci, John; Giroux, André; Zhu, Yanxia; Boucher, Mathieu; Pikounis, Bill; Xanthoudakis, Steven; Roy, Sophie; Rigby, Michael; Zamboni, Robert; Robertson, George S; Ng, Gordon Y K; Nicholson, Donald W; Flückiger, Jean-Pierre

    2004-01-01

    Caspases, key enzymes in the apoptosis pathway, have been detected in the brain of HD patients and in animal models of the disease. In the present study, we investigated the neuroprotective properties of a new, reversible, caspase-3-specific inhibitor, M826 (3-({(2S)-2-[5-tert-butyl-3-{[(4-methyl-1,2,5-oxadiazol-3-yl)methyl]amino}-2-oxopyrazin-1(2H)-yl]butanoyl}amino)-5-[hexyl(methyl)amino]-4-oxopentanoic acid), in a rat malonate model of HD. Pharmacokinetic and autoradiography studies after intrastriatal (i.str.) injection of 1.5 nmol of M826 or its tritiated analogue [3H]M826 indicated that the compound diffused within the entire striatum. The elimination half-life (T1/2) of M826 in the rat striatum was 3 h. I.str. injection of 1.5 nmol of M826 10 min after malonate infusion induced a significant reduction (66%) in the number of neurones expressing active caspase-3 in the ipsilateral striatum. Inhibition of active caspase-3 translated into a significant but moderate reduction (39%) of the lesion volume, and of cell death (24%), 24 h after injury. The efficacy of M826 at inhibiting cell death was comparable to that of the noncompetitive NMDA receptor antagonist MK801. These data provide in vivo proof-of-concept of the neuroprotective effects of reversible caspase-3 inhibitors in a model of malonate-induced striatal injury in the adult rat. PMID:14744804

  3. Neuroprotective effects of M826, a reversible caspase-3 inhibitor, in the rat malonate model of Huntington's disease.

    PubMed

    Toulmond, Sylvie; Tang, Keith; Bureau, Yves; Ashdown, Helen; Degen, Sarah; O'Donnell, Ruth; Tam, John; Han, Yongxin; Colucci, John; Giroux, André; Zhu, Yanxia; Boucher, Mathieu; Pikounis, Bill; Xanthoudakis, Steven; Roy, Sophie; Rigby, Michael; Zamboni, Robert; Robertson, George S; Ng, Gordon Y K; Nicholson, Donald W; Flückiger, Jean-Pierre

    2004-02-01

    1. Caspases, key enzymes in the apoptosis pathway, have been detected in the brain of HD patients and in animal models of the disease. In the present study, we investigated the neuroprotective properties of a new, reversible, caspase-3-specific inhibitor, M826 (3-([(2S)-2-[5-tert-butyl-3-[[(4-methyl-1,2,5-oxadiazol-3-yl)methyl]amino]-2-oxopyrazin-1(2H)-yl]butanoyl]amino)-5-[hexyl(methyl)amino]-4-oxopentanoic acid), in a rat malonate model of HD. 2. Pharmacokinetic and autoradiography studies after intrastriatal (i.str.) injection of 1.5 nmol of M826 or its tritiated analogue [(3)H]M826 indicated that the compound diffused within the entire striatum. The elimination half-life (T(1/2)) of M826 in the rat striatum was 3 h. 3. I.str. injection of 1.5 nmol of M826 10 min after malonate infusion induced a significant reduction (66%) in the number of neurones expressing active caspase-3 in the ipsilateral striatum. 4. Inhibition of active caspase-3 translated into a significant but moderate reduction (39%) of the lesion volume, and of cell death (24%), 24 h after injury. The efficacy of M826 at inhibiting cell death was comparable to that of the noncompetitive NMDA receptor antagonist MK801. 5. These data provide in vivo proof-of-concept of the neuroprotective effects of reversible caspase-3 inhibitors in a model of malonate-induced striatal injury in the adult rat. PMID:14744804

  4. Minocycline fails to protect cerebellar granular cell cultures against malonate-induced cell death.

    PubMed

    Fernandez-Gomez, F J; Gomez-Lazaro, M; Pastor, D; Calvo, S; Aguirre, N; Galindo, M F; Jordán, J

    2005-11-01

    Experimental and clinical studies support the view that the semisynthetic tetracycline minocycline exhibits neuroprotective roles in several models of neurodegenerative diseases, including ischemia, Huntington, Parkinson diseases, and amyotrophic lateral sclerosis. However, recent evidence indicates that minocycline does not always present beneficial actions. For instance, in an in vivo model of Huntington's disease, it fails to afford protection after malonate intrastriatal injection. Moreover, it reverses the neuroprotective effect of creatine in nigrostriatal dopaminergic neurons. This apparent contradiction prompted us to analyze the effect of this antibiotic on malonate-induced cell death. We show that, in rat cerebellar granular cells, the succinate dehydrogenase inhibitor malonate induces cell death in a concentration-dependent manner. By using DFCA, monochlorobimane and 10-N-nonyl-Acridin Orange to measure, respectively, H2O2-derived oxidant species and reduced forms of GSH and cardiolipin, we observed that malonate induced reactive oxygen species (ROS) production to an extent that surpasses the antioxidant defense capacity of the cells, resulting in GSH depletion and cardiolipin oxidation. The pre-treatment for 4 h with minocycline (10-100 microM) did not present cytoprotective actions. Moreover, minocycline failed to block ROS production and to abrogate malonate-induced oxidation of GSH and cardiolipin. Additional experiments revealed that minocycline was also unsuccessful to prevent the mitochondrial swelling induced by malonate. Furthermore, malonate did not induce the expression of the iNOS, caspase-3, -8, and -9 genes which have been shown to be up-regulated in several models where minocycline resulted cytoprotective. In addition, malonate-induced down-regulation of the antiapoptotic gene Bcl-2 was not prevented by minocycline, controversially the mechanism previously proposed to explain minocycline protective action. These results suggest that the

  5. Hydrogen bonded structures in organic amine oxalates

    NASA Astrophysics Data System (ADS)

    Vaidhyanathan, R.; Natarajan, S.; Rao, C. N. R.

    2002-05-01

    Oxalates of n-propylamine, n-butylamine, ethylenediamine, 1,4-butanediamine, piperazine, guanidine and 1,4-diazabicyclo[2,2,2]octane (DABCO) have been synthesized and characterized by single crystal X-ray diffraction and other techniques. The amine oxalates show different types of hydrogen bonded networks, linear hydrogen bonded chains characterizing the oxalates of the first five amines. Guanidinium oxalate has a sheet like structure while DABCO oxalate has dimeric hydrogen bonded rings. Hydrogen bonded structures of these oxalates are discussed in detail, besides relating their thermal stability to the strengths of the networks.

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

    DOE PAGESBeta

    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.

  7. Metamagnetism and weak ferromagnetism in nickel (II) oxalate crystals

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  8. Metamagnetism and weak ferromagnetism in nickel (II) oxalate crystals.

    PubMed

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

    2012-05-16

    Microcrystals of orthorhombic nickel (II) oxalate dihydrate were synthesized through a precipitation reaction of aqueous solutions of nickel chloride and oxalic acid. Magnetic susceptibility exhibits a sharp peak at 3.3 K and a broad rounded maximum near 43 K. We associated the lower maximum with a metamagnetic transition that occurs when the magnetic field is about ≥3.5 T. The maximum at 43 K is typical of 1D antiferromagnets, whereas weak ferromagnetism behavior was observed in the range of 3.3–43 K. PMID:22517212

  9. New EPSP synthase inhibitors: synthesis and evaluation of an aromatic tetrahedral intermediate mimic containing a 3-malonate ether as a 3-phosphate surrogate.

    PubMed

    Miller, M J; Cleary, D G; Ream, J E; Snyder, K R; Sikorski, J A

    1995-12-01

    A new analog of the EPSP synthase enzyme reaction intermediate 1, containing a 3-malonate ether moiety in place of the usual 3-phosphate group, was synthesized from 3,5-dihydroxybenzoic acid. This simple, synthetically accessible aromatic compound (5) is an effective competitive inhibitor versus S3P with an apparent Ki of 1.3 +/- 0.22 microM. This result demonstrates that a simple benzene ring can be a suitable achiral substitute for the more complex shikimate ring in the design of EPSP synthase inhibitors. Furthermore, the greater potency of 5 versus the phenol 6, glycolate 7 and the gallic acid analog 8 demonstrates the requirement for multiple anionic charges at the dihydroxybenzoate 5-position in order to attain effective inhibition of this enzyme. However, this 3-malonate ether substituted compound was at least 10-fold less effective as a bisubstrate inhibitor than the corresponding 3-phosphate. This suggests that tetrahedral intermediate mimics possessing a 3-malonate ether moiety are less effective than their corresponding 3-phosphates in accessing the optimal enzyme conformation stabilizing 1. PMID:8770393

  10. 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.

  11. 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

  12. Protection of Metal Artifacts with the Formation of Metal–Oxalates Complexes by Beauveria bassiana

    PubMed Central

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

    2012-01-01

    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

  13. Oxalic acid supported Si-18F-radiofluorination: one-step radiosynthesis of N-succinimidyl 3-(di-tert-butyl[18F]fluorosilyl)benzoate ([18F]SiFB) for protein labeling.

    PubMed

    Kostikov, Alexey P; Chin, Joshua; Orchowski, Katy; Niedermoser, Sabrina; Kovacevic, Miriam M; Aliaga, Antonio; Jurkschat, Klaus; Wängler, Bjoern; Wängler, Carmen; Wester, Hans-Jürgen; Schirrmacher, Ralf

    2012-01-18

    N-Succinimidyl 3-(di-tert-butyl[(18)F]fluorosilyl)benzoate ([(18)F]SiFB), a novel synthon for one-step labeling of proteins, was synthesized via a simple (18)F-(19)F isotopic exchange. A new labeling technique that circumvents the cleavage of the highly reactive active ester moiety under regular basic (18)F-labeling conditions was established. In order to synthesize high radioactivity amounts of [(18)F]SiFB, it was crucial to partially neutralize the potassium oxalate/hydroxide that was used to elute (18)F(-) from the QMA cartridge with oxalic acid to prevent decomposition of the active ester moiety. Purification of [(18)F]SiFB was performed by simple solid-phase extraction, which avoided time-consuming HPLC and yielded high specific activities of at least 525 Ci/mmol and radiochemical yields of 40-56%. In addition to conventional azeotropic drying of (18)F(-) in the presence of [K(+)⊂2.2.2.]C(2)O(4), a strong anion-exchange (SAX) cartridge was used to prepare anhydrous (18)F(-) for nucleophilic radio-fluorination omitting the vacuum assisted drying of (18)F(-). Using a lyophilized mixture of [K(+)⊂2.2.2.]OH resolubilized in acetonitrile, the (18)F(-) was eluted from the SAX cartridge and used directly for the [(18)F]SiFB synthesis. [(18)F]SiFB was applied to the labeling of various proteins in likeness to the most commonly used labeling synthon in protein labeling, N-succinimidyl-4-[(18)F]fluorobenzoate ([(18)F]SFB). Rat serum albumin (RSA), apo-transferrin, a β-cell-specific single chain antibody, and erythropoietin were successfully labeled with [(18)F]SiFB in good radiochemical yields between 19% and 36%. [(18)F]SiFB- and [(18)F]SFB-derivatized RSA were directly compared as blood pool imaging agents in healthy rats using small animal positron emission tomography. Both compounds demonstrated identical biodistributions in healthy rats, accurately visualizing the blood pool with PET. PMID:22148255

  14. 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.

  15. 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.

  16. 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.

  17. Inhibition of crystallization of calcium oxalate by the extraction of Tamarix gallica L.

    PubMed

    Bensatal, Ahmed; Ouahrani, M R

    2008-12-01

    The main objective is to study the inhibitor effect of acid fraction of the extract of Tamarix gallica L on the crystallization of calcium oxalate. The extract of Tamarix gallica L is very rich by acid compounds that are used as an inhibitor of nephrolithiasis (calcium oxalate). Our study of the calcium oxalate crystallization is based on the model of turbidimetry by means of a spectrophotometer. The calcium oxalate formation is induced by the addition of oxalate solutions of sodium and of calcium chloride. The addition of inhibitor with various concentrations enabled us to give information on the percentage of inhibition. The comparison between the turbidimetric slopes with and without inhibitor gives the effectiveness of inhibitor for the acid fraction. By comparing the photographs of with and without inhibitor, we concluded that the extract of Tamarix gallica L acts at the stage of growth. The acid fraction of the extract of Tamarix gallica L gives an activity remarkable in the formation of urinary lithiasis (calcium oxalate); this effectiveness is due to the presence of functions of acid. PMID:19002446

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. Aluminum(III) speciation with acetate and oxalate. A potentiometric and sup 27 Al NMR study

    SciTech Connect

    Thomas, F.; Rouiller, J.; Genevrier, F.; Boudot, D. ); Masion, A.; Bottero, J.Y. )

    1991-09-01

    Aluminum (III) hydrolysis and precipitation in the presence of acetic acid and oxalic acid have been studied by combining potentiometric titration and liquid-state {sup 27}Al NMR. The main aluminum species have thus been identified and quantified: unreacted hydrolyzed, complexed monomers, and the Al{sub 13} tridecamer. A solid species appeared when precipitation occurred and was quantified by difference with the other species. The quantitative evolution of these species was followed for pH values up to 5. Acetate forms weak complexes with aluminum. The precipitated phase was hypothesized to be aggregated Al{sub 13}. Oxalate forms strong multiligand complexes to form Al{sub 13} requires higher hydroxyl content. High oxalate contents (L/M > 1) inhibit tridecamer formation and precipitation occurs only at high pH values. With oxalate the precipitated phase seems to be devoid of Al{sub 13} and of a more condensed nature than it is with acetate.

  3. Stability Constants of Technetium (IV) Oxalate Complexes as a Function of Ionic Strength

    SciTech Connect

    Xia, Yuanxian; Hess, Nancy J.; Felmy, Andrew R.

    2006-03-01

    Solvent extraction methods were used to determine the stability constants of Tc(IV) with oxalate anions in NaCl solutions ranging in concentration from 0.5 M to 2.0 M. All experiments were conducted in an atmosphere-controlled chamber under Ar atmosphere (< 1.0ppm O2). A reducing agent (hydrazine) was used during extractions to maintain technetium in the tetravalent oxidation state. Independent tests confirmed that the oxidation state of technetium did not change during extractions. The distribution ratio of Tc(IV) between the organic and aqueous phases was found to decrease as the concentration of oxalic acid increased. At the oxalic acid concentrations used in these experiments, the complexes TcO(Ox) and TcO(Ox)22- were found to be the dominant aqueous species. Based on these data, the thermodynamic stability constants of Tc(IV) with oxalate complexes were calculated by the Specific Ion Interaction Theory (SIT).

  4. 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.

  5. 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 ...

  6. Comparative biosorption of Mn(II) and Pb(II) ions on raw and oxalic acid modified maize husk: kinetic, thermodynamic and isothermal studies

    NASA Astrophysics Data System (ADS)

    Adeogun, Abideen Idowu; Idowu, Mopelola Abidemi; Ofudje, Andrew Edwin; Kareem, Sarafadeen Olateju; Ahmed, Sikiru Akinyeye

    2013-03-01

    Maize husk, an abundant agricultural waste was used to prepare a biosorbent for the biosorption of Mn(II) and Pb(II) ions from aqueous solution in a batch process. Equilibrium and kinetics of biosorption of the metals ions were studied at 25 °C. The adsorbtion data were treated with common kinetic and isotherm models. The equilibrium data fitted well with Langmuir isotherm with maximum capacity of 8.52 and 7.38 mg g-1 for Mn(II) and Pb(II), respectively on raw biomass (UTCS). The capacity of 9.00 and 9.33 mg g-1 was observed for Mn(II) and Pb(II), respectively on acid modified biomass (ATCS). The study also revealed that the sorption process in both cases depend on biomass dosage, temperature, pH and initial metal ion concentration, respectively. The calculated thermodynamic parameters (∆ G o, ∆ H o and ∆ S o) showed that the biosorption of the metal ions onto maize husk is feasible, spontaneous and exothermic in nature.

  7. 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

  8. 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

  9. Genome-Wide Screen for Oxalate-Sensitive Mutants of Saccharomyces cerevisiae▿ †

    PubMed Central

    Cheng, V.; Stotz, H. U.; Hippchen, K.; Bakalinsky, A. T.

    2007-01-01

    Oxalic acid is an important virulence factor produced by phytopathogenic filamentous fungi. In order to discover yeast genes whose orthologs in the pathogen may confer self-tolerance and whose plant orthologs may protect the host, a Saccharomyces cerevisiae deletion library consisting of 4,827 haploid mutants harboring deletions in nonessential genes was screened for growth inhibition and survival in a rich medium containing 30 mM oxalic acid at pH 3. A total of 31 mutants were identified that had significantly lower cell yields in oxalate medium than in an oxalate-free medium. About 35% of these mutants had not previously been detected in published screens for sensitivity to sorbic or citric acid. Mutants impaired in endosomal transport, the rgp1Δ, ric1Δ, snf7Δ, vps16Δ, vps20Δ, and vps51Δ mutants, were significantly overrepresented relative to their frequency among all verified yeast open reading frames. Oxalate exposure to a subset of five mutants, the drs2Δ, vps16Δ, vps51Δ, ric1Δ, and rib4Δ mutants, was lethal. With the exception of the rib4Δ mutant, all of these mutants are impaired in vesicle-mediated transport. Indirect evidence is provided suggesting that the sensitivity of the rib4Δ mutant, a riboflavin auxotroph, is due to oxalate-mediated interference with riboflavin uptake by the putative monocarboxylate transporter Mch5. PMID:17644632

  10. 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

  11. 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

  12. 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.

  13. 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

  14. Glyoxylate rather than ascorbate is an efficient precursor for oxalate biosynthesis in rice

    PubMed Central

    Yu, Le; Jiang, Jingzhe; Zhang, Chan; Jiang, Linrong; Ye, Nenghui; Lu, Yusheng; Yang, Guozheng; Liu, Ee; Peng, Changlian; He, Zhenghui; Peng, Xinxiang

    2010-01-01

    Oxalate is widely distributed in the plant kingdom. While excess oxalate in food crops is detrimental to animal and human health, it may play various functional roles in plants, particularly for coping with environmental stresses. Understanding its biosynthetic mechanism in plants, therefore, becomes increasingly important both theoretically and practically. However, it is still a matter of debate as to what precursor and pathway are ultimately used for oxalate biosynthesis in plants. In this study, both physiological and molecular approaches were applied to address these questions. First, it was observed that when glycolate or glyoxylate was fed into detached leaves, both organic acids were equally effective in stimulating oxalate accumulation. In addition, the stimulation could be completely inhibited by cysteine, a glyoxylate scavenger that forms cysteine–glyoxylate adducts. To verify the role of glyoxylate further, various transgenic plants were generated, in which several genes involved in glyoxylate metabolism [i.e. SGAT (serine-glyoxylate aminotransferase), GGAT (glutamate-glyoxylate aminotransferase), HPR (hydroxypyruvate reductase), ICL (isocitrate lyase)], were transcriptionally regulated through RNAi or over-expression. Analyses on these transgenic plants consistently revealed that glyoxylate acted as an efficient precursor for oxalate biosynthesis in rice. Unexpectedly, it was found that oxalate accumulation was not correlated with photorespiration, even though this pathway is known to be a major source of glyoxylate. Further, when GLDH (L-galactono-1,4-lactone dehydrogenase), a key enzyme gene for ascorbate biosynthesis, was down-regulated, the oxalate abundance remained constant, despite ascorbate having been largely reduced as expected in these transgenic plants. Taken together, our results strongly suggest that glyoxylate rather than ascorbate is an efficient precursor for oxalate biosynthesis, and that oxalate accumulation and regulation do not

  15. EPR Spin Trapping of an Oxalate-Derived Free Radical in the Oxalate Decarboxylase Reaction

    PubMed Central

    Imaram, Witcha; Saylor, Benjamin T.; Centonze, Christopher P.; Richards, Nigel G. J.; Angerhofer, Alexander

    2011-01-01

    EPR spin trapping experiments on bacterial oxalate decarboxylase from Bacillus subtilis under turn-over conditions are described. The use of doubly 13C-labeled oxalate leads to a characteristic splitting of the observed radical adducts using the spin trap N-tert-butyl-α-phenylnitrone linking them directly to the substrate. The radical was identified as the carbon dioxide radical anion which is a key intermediate in the hypothetical reaction mechanism of both decarboxylase and oxidase activities. X-ray crystallography had identified a flexible loop, SENS161-4, which acts as a lid to the putative active site. Site directed mutagenesis of the hinge amino acids, S161 and T165 was explored and showed increased radical trapping yields compared to the wild type. In particular, T165V shows approximately ten times higher radical yields while at the same time its decarboxylase activity was reduced by about a factor of ten. This mutant lacks a critical H-bond between T165 and R92 resulting in compromised control over its radical chemistry allowing the radical intermediate to leak into the surrounding solution. PMID:21277974

  16. 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

  17. 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.

  18. 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 ...

  19. 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...

  20. 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.

  1. Dissolution kinetics and biodurability of tremolite particles in mimicked lung fluids: Effect of citrate and oxalate

    NASA Astrophysics Data System (ADS)

    Rozalen, Marisa; Ramos, M. Elena; Huertas, F. Javier; Fiore, Saverio; Gervilla, Fernando

    2013-11-01

    The effect of citrate and oxalate on tremolite dissolution rate was measured at 37 °C in non-stirred flow-through reactors, using modified Gamble's solutions at pH 4 (macrophages), 7.4 (interstitial fluids) and 5.5 (intermediate check point) containing 0, 0.15, 1.5 and 15 mmol L-1 of citrate or oxalate. The dissolution rates calculated from Si concentration in the output solutions without organic ligands depend on pH, decreasing when the pH increases from -13.00 (pH 4) to -13.35 (pH 7.4) mol g-1 s-1 and following a proton-promoted mechanism. The presence of both ligands enhances dissolution rates at every pH, increasing this effect when the ligand concentration increases. Citrate produces a stronger effect as a catalyst than oxalate, mainly at more acidic pHs and enhances dissolution rates until 20 times for solutions with 15 mmol L-1 citrate. However, at pH 7.4 the effect is lighter and oxalate solutions (15 mmol L-1) only enhances dissolution rates eight times respect to free organic ligand solutions. Dissolution is promoted by the attack to protons and organic ligands to the tremolite surface. Magnesium speciation in oxalate and citrate solutions shows that Mg citrate complexes are more effective than oxalate ones during the alteration of tremolite in magrophages, but this tendency is the opposite for interstitial fluids, being oxalate magnesium complexes stronger. The biodurability estimations show that the destruction of the fibers is faster in acidic conditions (macrophages) than in the neutral solutions (interstitial fluid). At pH 4, both ligands oxalate and citrate reduce the residence time of the fibers with respect to that calculated in absence of ligands. Nevertheless, at pH 7.4 the presence of ligands does not reduce significantly the lifetime of the fibers.

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  3. 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

  4. 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.

  5. Influence of hydrochlorothiazide on urinary calcium oxalate relative supersaturation in healthy young adult female domestic shorthaired cats.

    PubMed

    Hezel, Alisha; Bartges, Joseph W; Kirk, Claudia A; Cox, Sherry; Geyer, Nicole; Moyers, Tammy; Hayes, Jimmy

    2007-01-01

    Hydrochlorothiazide (1 mg/kg PO q12h) or placebo was administered to healthy cats for 2 weeks in a masked, placebo-controlled, crossover-design study, and 24-hour urine samples were collected. When cats received hydrochlorothiazide, 24-hour urine volume, ammonia, chloride, creatinine, magnesium, oxalic acid, phosphate, potassium, and sodium were significantly higher than when cats received placebo. Hydrochlorothiazide was associated with significantly lower urinary saturation for calcium oxalate, but no difference was found in 24-hour urine calcium and citrate, urinary saturation for struvite, or blood ionized calcium. Hydrochlorothiazide decreased urinary saturation for calcium oxalate and could be useful in managing cats with calcium oxalate uroliths. Results of this study, however, should not be extrapolated to cats that form calcium oxalate uroliths. PMID:18183543

  6. 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

  7. Ultrastructural and biochemical studies on formation of calcium oxalate in plants

    SciTech Connect

    Abdelmottaleb, A.M.

    1989-01-01

    Plant calcium oxalate crystals occur within cells called crystal idioblasts. Important aspects of this calcification phenomenon have not been characterized. This dissertation examines some of the aspects of this ubiquitous type of calcification including (1) characterization of ultrastructural features of developing crystal idioblasts, (2) determination of the relationship of specialized ultrastructural features of the idioblasts to transport of compounds and mechanisms of crystal deposition, and (3) the biochemical relationship between ascorbic acid metabolism and production of oxalic acid used for crystal formation. Structural and cytochemical studies revealed that crystal idioblasts have dense cytoplasm, modified plastids, enlarged nuclei, extensive endoplasmic reticulum, numerous dictyosomes and vesicles, and a bundle of raphide crystals in their vacuoles. A mechanism for Ca transport and crystal precipitation is proposed, based on these results. There is a strong and dynamic relationship between Ca concentration and oxalic acid produced for crystal formation, where increasing Ca level in the growth medium lead to increased total and insoluble oxalate in the plant. Calmodulin antagonists reduced oxalic acid production.

  8. 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

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

    SciTech Connect

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

    1987-01-01

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

  10. 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.

  11. 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.

  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. PMID:27219322

  13. 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.

  14. Computational study on nitronium and nitrosonium oxalate: potential oxidizers for solid rocket propulsion?

    PubMed

    Gökçinar, Elif; Klapötke, Thomas M; Kramer, Michael P

    2010-08-26

    The enthalpies of formation for solid ionic nitrosonium oxalate, [NO](2)[O(2)C-CO(2)], nitronium oxalate, [NO(2)](2)[O(2)C-CO(2)], as well as covalent bis(nitroso)oxalic acid, ON-O(2)C-CO(2)-NO, and oxalic acid dinitrate ester, O(2)N-O(2)C-CO(2)-NO(2), were calculated using the complete basis set (CBS-4M) method of Petersson and coworkers to obtain very accurate energies. For the nitrosonium species, the ionic form ([NO](2)[O(2)C-CO(2)]) was identified as the more stable isomer, whereas for the nitrosonium compound, the covalently bound dinitrate ester (O(2)N-O(2)C-CO(2)-NO(2)) was found to be more stable. The combustion parameters with respect to possible use as ingredients in solid rocket motors for both stable species were calculated using the EXPLO5 and the ICT code. The performance of an aluminized formulation with covalently bound dinitrate ester (O(2)N-O(2)C-CO(2)-NO(2)) was shown to be comparable to that of ammonium perchlorate/aluminum. This makes oxalic acid dinitrate ester a potentially interesting perchlorate-free and environmentally benign oxidizer for solid rocket propulsion. PMID:20302312

  15. Removal of azo dye C.I. acid red 14 from contaminated water using Fenton, UV/H(2)O(2), UV/H(2)O(2)/Fe(II), UV/H(2)O(2)/Fe(III) and UV/H(2)O(2)/Fe(III)/oxalate processes: a comparative study.

    PubMed

    Daneshvar, N; Khataee, A R

    2006-01-01

    The decolorization of the solution containing a common textile and leather dye, C.I. Acid Red 14 (AR14), at pH 3 by hydrogen peroxide photolysis, Fenton, Fenton-like and photo-Fenton processes was studied. The dark and light reactions were carried out in stirred batch photoreactor equipped with an UV-C lamp (30 W) as UV light source. The experiments showed that the dye was resistant to the UV illumination, but was oxidized when one of Fe(II), Fe(III) and H(2)O(2) compounds was present. It was also found that UV light irradiation can accelerate significantly the rate of AR14 decolorization in the presence of Fe(III)/H(2)O(2) or Fe(II)/H(2)O(2), comparing to that in the dark. The effect of different system variables like initial concentration of the azo dye, effect of UV light irradiation, initial concentration of Fe(II) or Fe(III) and added oxalate ion has been investigated. The results showed that the decolorization efficiency of AR14 at the reaction time of 2 min follows the decreasing order: UV/H(2)O(2)/Fe(III)/oxalate > UV/H(2)O(2)/Fe(III) > UV/H(2)O(2)/Fe(II) > UV/H(2)O(2). Our results also showed that the UV/H(2)O(2)/Fe(III)/oxalate process was appropriate as the effective treatment method for decolorization of a real dyeing and finishing. The mechanism for each process is also discussed and linked together for understanding the observed differences in reactivity. PMID:16484066

  16. 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

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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

  19. Volatile aromatic hydrocarbons and dicarboxylic acid concentrations in air at an urban site in the Southwestern US

    NASA Astrophysics Data System (ADS)

    Tran, Ngoc K.; Steinberg, Spencer M.; Johnson, Brian J.

    Concentrations of benzene, toluene, ethylbenzene, o-xylene, and m- and p-xylene were measured at an urban sampling site in Las Vegas, NV by sorbent sampling followed by thermal desorption and determination by GC-PID. Simultaneously, measurements of oxalic, malonic, succinic, and adipic acids were made at the same site by collection on quartz filters, extraction, esterification, and determination by GC-FID. For the period from April 7, 1997 to June 11, 1997, 201 sets of hydrocarbon measurements and 99 sets of acid measurements were made. Additional measurements of dicarboxylic acids were made on samples that represented potential direct sources, e.g. green plants and road dust. Correlations between the hydrocarbon and CO concentrations (measured by the Clark County Health District at a nearby site) were highly significant and a strong negative correlation of hydrocarbon concentration with ozone concentration (also from the county site) was observed under quiescent atmospheric conditions. In general, dicarboxylic acid concentrations were well correlated with one another (with the exception of adipic acid) but not well correlated with hydrocarbon, CO, and ozone concentrations. Multiple sources and complex formation processes are indicated for the dicarboxylic acids.

  20. 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

  1. 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. PMID:23149251

  2. Spectral, electrochemical and molecular orbital studies on solvatochromic mixed ligand copper(II) complexes of malonate and diamine derivatives

    NASA Astrophysics Data System (ADS)

    Taha, Ali

    2003-04-01

    Solvatochromic mixed ligand complexes of copper(II) with malonate and diamine derivatives, Cu n(RMal)(diam) nXm (where n=1 or 2, m=1-4, RMal, malonic acid (H 2Mal), diethylmalonate (HDEtMal) or diethylethoxyethylenemalonate (DEtEMal), and diam, ethylenediamine (en), 1,3-propylenediamine (1,3-pn), N, N, N'-trimethylethylenediamine (Me 3en), N, N, N'-triethylethylenediamine (Et 3en), N, N, N', N'-tetramethylethylenediamine (Me 4en), N, N, N', N'-tetramethylpropylenediamine (Me 4pn), or N-methyl-1,4-diazacycloheptane (medach); and X=ClO 4- or Cl -), has been synthesized and characterized by spectroscopic, magnetic, molar conductance and electrochemical measurements. The mass spectra along with the analytical data of the complexes show peaks with m/ e corresponding to a bridged binuclear structure for the chloride complexes, while perchlorate complexes showed either mononuclear structure for DEtMal and DEtEMal or bridged binuclear structure for Mal complexes. These results correspond to IR spectral data, which indicated that the modes of ester and carboxylato coordination sites are mono- and/or bidentate. The d-d absorption bands in weak donor solvents suggest square-planar and distorted square pyramidal-trigonal bipyramid geometries for the perchlorate and chloride complexes; respectively. On the other hand, an octahedral structure is identified for complexes in strong donor solvents. Perchlorate complexes show a drastic color change from violet to green as the donation ability of solvent increases, whereas chloride complexes are highly affected by the acceptor properties of the solvent. Cyclic voltammetric measurements on the complexes, proposed a quasi-reversible or irreversible and mainly diffusion controlled reduction process. Such behavior has been explained according to the ECE mechanism. A linear correlation has been found between the Cu(II) reduction potential and the spectral data. Molecular orbital calculations were performed for the ligands on the bases of

  3. 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

  4. 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

  5. Chronic metabolic acidosis reduces urinary oxalate excretion and promotes intestinal oxalate secretion in the rat.

    PubMed

    Whittamore, Jonathan M; Hatch, Marguerite

    2015-11-01

    Urinary oxalate excretion is reduced in rats during a chronic metabolic acidosis, but how this is achieved is not clear. In this report, we re-examine our prior work on the effects of a metabolic acidosis on urinary oxalate handling [Green et al., Am J Physiol Ren Physiol 289(3):F536-F543, 2005], offering a more detailed analysis and interpretation of the data, together with new, previously unpublished observations revealing a marked impact on intestinal oxalate transport. Sprague-Dawley rats were provided with 0.28 M ammonium chloride in their drinking water for either 4 or 14 days followed by 24 h urine collections, blood-gas and serum ion analysis, and measurements of (14)C-oxalate fluxes across isolated segments of the distal colon. Urinary oxalate excretion was significantly reduced by 75% after just 4 days compared to control rats, and this was similarly sustained at 14 days. Oxalate:creatinine clearance ratios indicated enhanced net re-absorption of oxalate by the kidney during a metabolic acidosis, but this was not associated with any substantive changes to serum oxalate levels. In the distal colon, oxalate transport was dramatically altered from net absorption in controls (6.20 ± 0.63 pmol cm(-2) h(-1)), to net secretion in rats with a metabolic acidosis (-5.19 ± 1.18 and -2.07 ± 1.05 pmol cm(-2) h(-1) at 4 and 14 days, respectively). Although we cannot rule out modifications to bi-directional oxalate movements along the proximal tubule, these findings support a gut-kidney axis in the management of oxalate homeostasis, where this shift in renal handling during a metabolic acidosis is associated with compensatory adaptations by the intestine. PMID:26162424

  6. 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.

  7. Isolation and characterization of mesophilic, oxalate-degrading Streptomyces from plant rhizosphere and forest soils.

    PubMed

    Sahin, Nurettin

    2004-10-01

    The present work was aimed at the isolation of additional new pure cultures of oxalate-degrading Streptomyces and its preliminary characterization for further work in the field of oxalate metabolism and taxonomic studies. Mesophilic, oxalate-degrading Streptomyces were enriched and isolated from plant rhizosphere and forest soil samples. Strains were examined for cultural, morphological (spore chain morphology, spore mass colour, diffusible and melanin pigment production), physiological (antibiosis, growth in the presence of inhibitory compounds, assimilation of organic acids and enzyme substrates) and chemotaxonomic characters (cellular lipid components and diagnostic cell-wall diamino acid). The taxonomic data obtained were analysed by using the simple matching (SSM) and Jaccard (Sj) coefficients, clustering was achieved using the UPGMA algorithm. All strains were able to utilize sodium-, potassium-, calcium- and ammonium-oxalate salts. Based on the results of numerical taxonomy, isolates were grouped into five cluster groups with a > or =70% S(SM) similarity level. Streptomyces rochei was the most common of the cluster groups, with a Willcox probability of P > 0.8. Streptomyces antibioticus, S. anulatus, S. fulvissimus, S. halstedii and S. violaceusniger are newly reported as oxalate-utilizing Streptomyces. PMID:15448922

  8. 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

  9. 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.

  10. Malone Antegrade Continence Enema in Patients with Perineal Colostomy After Rectal Resection.

    PubMed

    Wang, Jin-Hai; Xu, Jia-He; Ye, Feng; Xu, Xiang-Ming; Lin, Jian-Jiang; Chen, Wen-Bin

    2015-12-01

    The objective of this study was to evaluate the value of antegrade continence enema (Malone operation) in abdominoperineal resection (Miles' operation). Between January 2008 and May 2009, five cancer patients (two men and three women) underwent abdominoperineal resection and digestive reconstruction by perineal colostomy and Malone antegrade continence enema in our institution. Their functional results and quality of life were recorded. None of the patients died, but two had wound infections and one experienced urinary retention. Patients performed antegrade enema every 24 h with 2,000 mL of normal saline by themselves. The duration of the enema lasted for an average of approximately 35 min, and fecal contamination was not detected at 24 h. Patient satisfaction was determined to be 88 %. Malone antegrade continence enema associated with abdominoperineal resection and perineal colostomy provided acceptable continence. It preserved the body image of the patients and resulted in a satisfactory quality of life. It is a potential alternative for patients who are not willing to have a permanent colostomy. PMID:26730081

  11. 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.

  12. Effects of oxalate exposure on Madin-Darby canine kidney cells in culture: renal prothrombin fragment-1 mRNA expression.

    PubMed

    Moryama, Manabu T; Domiki, Chizue; Miyazawa, Katsuhito; Tanaka, Tatsuro; Suzuki, Koji

    2005-12-01

    It has been suggested that renal tubular cell damage induced by oxalic acid, one of the components of urinary calculi, may be involved in a variety of ways in the development of urolithiasis. During our study on a calculus related protein, renal prothrombin fragment-1 (RPTF-1), we noted that this is an inflammation related substance that mediates an acute inflammatory reaction, one of the original roles of prothrombin. RPTF-1 is a part of prothrombin that is a coagulation factor known to be expressed in the renal tubule. We examined whether oxalic acid may cause cytotoxic effects on tubular epithelial cells and whether such chemical stimulation may promote the translation of RPTF-1 mRNA into RPTF-1 proteins. We used Madin-Darby canine kidney (MDCK) cells derived from the distal tubule of a dog kidney. In this study, the effects of oxalic acid in culture solution at different concentrations on cytotoxicity were assessed using a MTT assay. The location of active oxygen species was identified using dichlorofluorescein diacetate. After the prothrombin sequence of RPTF-1 was confirmed in MDCK cells, RPTF-1 mRNA expression was determined by RT-PCR. The gene sequence of the same promoter area was ligated, and a luciferase sequence was inserted downstream of the vector. The target sequence was transfected into MDCK cells and the relation between oxalic acid and prothrombin promoter was examined. In addition, the variable expression of RPTF-1 mRNA was quantitatively compared depending on oxalic acid concentrations using real-time PCR. When cytotoxicity was investigated, cells were not damaged but, by contrast, were stimulated and activated under oxalic acid below a certain concentration. The relation between cytotoxicity on the cultured MDCK cell membrane and active oxygen species was confirmed. Luminescence in MDCK cells containing the luciferase gene was detected by the addition of oxalic acid, which activated the prothrombin promoter. A part of the prothrombin gene

  13. 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

  14. 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. PMID:26517544

  15. 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

  16. Cadmium-induced oxalate secretion from root apex is associated with cadmium exclusion and resistance in Lycopersicon esulentum.

    PubMed

    Zhu, Xiao Fang; Zheng, Cheng; Hu, Yi Ting; Jiang, Tao; Liu, Yu; Dong, Ning Yu; Yang, Jian Li; Zheng, Shao Jian

    2011-07-01

    The mechanisms of heavy metal resistance in plants can be classified into internal tolerance and exclusion mechanisms, but exclusion of heavy metals with the help of organic acids secretion has not been well documented. Here we demonstrated the contribution of oxalate secretion to cadmium (Cd) exclusion and resistance in tomato. Different Cd resistance between two tomato cultivars was evaluated by relative root elongation (RRE) and Cd accumulation. Cultivar 'Micro-Tom' showed better growth and lower Cd content in roots than 'Hezuo903' at different Cd concentrations not only in short-term hydroponic experiment but also in long-term hydroponic and soil experiments, indicating that the genotypic difference in Cd resistance is related to the exclusion of Cd from roots. 'Micro-Tom' had greater ability to secrete oxalate, suggesting that oxalate secretion might contribute to Cd resistance. Cd-induced secretion of oxalate was localized to root apex at which the majority of Cd accumulated. Phenylglyoxal, an anion-channel inhibitor, effectively blocked Cd-induced oxalate secretion and aggravated Cd toxicity while exogenous oxalate supply ameliorated Cd toxicity efficiently. These results indicated that the oxalate secreted from the root apex helps to exclude Cd from entering tomato roots, thus contributes to Cd resistance in the Cd-resistant tomato cultivar. PMID:21388421

  17. Separation of americium, curium, and rare earths from high-level wastes by oxalate precipitation: experiments with synthetic waste solutions

    SciTech Connect

    Forsberg, C.W.

    1980-01-01

    The separation of trivalent actinides and rare earths from other fission products in high-level nuclear wastes by oxalate precipitation followed by ion exchange (OPIX) was experimentally investigated using synthetic wastes and a small-scale, continuous-flow oxalic acid precipitation and solid-liquid separation system. Trivalent actinide and rare earth oxalates are relatively insoluble in 0.5 to 1.0 M HNO/sub 3/ whereas other fission product oxalates are not. The continuous-flow system consisted of one or two stirred-tank reactors in series for crystal growth. Oxalic acid and waste solutions were mixed in the first tank, with the product solid-liquid slurry leaving the second tank. Solid-liquid separation was tested by filters and by a gravity settler. The experiments determined the fraction of rare earths precipitated and separated from synthetic waste streams as a function of number of reactors, system temperature, oxalic acid concentration, liquid residence time in the process, power input to the stirred-tank reactors, and method of solid-liquid separation. The crystalline precipitate was characterized with respect to form, size, and chemical composition. These experiments are only the first step in converting a proposed chemical flowsheet into a process flowsheet suitable for large-scale remote operations at high activity levels.

  18. Effect of oxalate on the dissolution rates of oligoclase and tremolite

    SciTech Connect

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

    1987-09-01

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

  19. 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

  20. 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.

  1. 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.

  2. A Potentiometric, Spectrophotometric and Pitzer Ion-Interaction Study of Reaction Equilibria in the Aqueous H+-Al3+, H+-Oxalate and H+-Al3+-Oxalate Systems up to 5 mol*dm-3 NaCl

    SciTech Connect

    Boily, Jean F.; Qafoku, Odeta; Felmy, Andrew R.

    2007-12-01

    Aluminium-oxalate complexation was determined in acidic media of aqueous NaCl solutions ranging from 0.1-5.0 mol•dm-3. Complexation in the H+-Al3+ and H+-Oxalate systems was also studied to provide a set of internally consistent thermodynamic data. The ionic strength dependent formation constants describing the stabilities of the Al3+, AlOH2+, Al3(OH)45+, Al13O4(OH)247+, H2L, HL-, L2-, AlL+, AlL2- and AlL33- species (where L is the oxalate ion) was also described using a Pitzer ion interaction model. The derived parameters can be used to predict chemical speciation in the H+-Al3+-Oxalate system in the 0.1-5.0 mol•dm-3 NaCl range.

  3. Purification and characterization of a cytoplasmic enzyme component of the Na+-activated malonate decarboxylase system of Malonomonas rubra: acetyl-S-acyl carrier protein: malonate acyl carrier protein-SH transferase.

    PubMed

    Hilbi, H; Dimroth, P

    1994-01-01

    Malonate decarboxylation by crude extracts of Malonomonas rubra was specifically activated by Na+ and less efficiently by Li+ ions. The extracts contained an enzyme catalyzing CoA transfer from malonyl-CoA to acetate, yielding acetyl-CoA and malonate. After about a 26-fold purification of the malonyl-CoA:acetate CoA transferase, an almost pure enzyme was obtained, indicating that about 4% of the cellular protein consisted of the CoA transferase. This abundance of the transferase is in accord with its proposed role as an enzyme component of the malonate decarboxylase system, the key enzyme of energy metabolism in this organism. The apparent molecular weight of the polypeptide was 67,000 as revealed from SDS-polyacrylamide gel electrophoresis. A similar molecular weight was estimated for the native transferase by gel chromatography, indicating that the enzyme exists as a monomer. Kinetic analyses of the CoA transferase yielded the following: pH-optimum at pH 5.5, an apparent Km for malonyl-CoA of 1.9mM, for acetate of 54mM, for acetyl-CoA of 6.9mM, and for malonate of 0.5mM. Malonate or citrate inhibited the enzyme with an apparent Ki of 0.4mM and 3.0mM, respectively. The isolated CoA transferase increased the activity of malonate decarboxylase of a crude enzyme system, in which part of the endogenous CoA transferase was inactivated by borohydride, about three-fold. These results indicate that the CoA transferase functions physiologically as a component of the malonate decarboxylase system, in which it catalyzes the transfer of acyl carrier protein from acetyl acyl carrier protein and malonate to yield malonyl acyl carrier protein and acetate. Malonate is thus activated on the enzyme by exchange for the catalytically important enzymebound acetyl thioester residues noted previously. This type of substrate activation resembles the catalytic mechanism of citrate lyase and citramalate lyase. PMID:18251085

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. Influence of nutrition on feline calcium oxalate urolithiasis with emphasis on endogenous oxalate synthesis.

    PubMed

    Dijcker, J C; Plantinga, E A; van Baal, J; Hendriks, W H

    2011-06-01

    The prevalence of calcium oxalate (CaOx) uroliths detected in cats with lower urinary tract disease has shown a sharp increase over the last decades with a concomitant reciprocal decrease in the occurrence of struvite (magnesium ammonium phosphate) uroliths. CaOx stone-preventative diets are available nowadays, but seem to be marginally effective, as CaOx urolith recurrence occurs in patients fed these diets. In order to improve the preventative measures against CaOx urolithiasis, it is important to understand its aetiopathogenesis. The main research focus in CaOx formation in cats has been on the role of Ca, whereas little research effort has been directed towards the role and origin of urinary oxalates. As in man, the exogenous origin of urinary oxalates in cats is thought to be of minor importance, although the precise contribution of dietary oxalates remains unclear. The generally accepted dietary risk factors for CaOx urolithiasis in cats are discussed and a model for the biosynthetic pathways of oxalate in feline liver is provided. Alanine:glyoxylate aminotransferase 1 (AGT1) in endogenous oxalate metabolism is a liver-specific enzyme targeted in the mitochondria in cats, and allows for efficient conversion of glyoxylate to glycine when fed a carnivorous diet. The low peroxisomal activity of AGT1 in cat liver is compatible with the view that felids utilised a low-carbohydrate diet throughout evolution. Future research should focus on understanding de novo biosynthesis of oxalate in cats and their adaptation(s) in oxalate metabolism, and on dietary oxalate intake and absorption by cats. PMID:21338551

  10. Isolation of a crystal matrix protein associated with calcium oxalate precipitation in vacuoles of specialized cells.

    PubMed

    Li, Xingxiang; Zhang, Dianzhong; Lynch-Holm, Valerie J; Okita, Thomas W; Franceschi, Vincent R

    2003-10-01

    The formation of calcium (Ca) oxalate crystals is considered to be a high-capacity mechanism for regulating Ca in many plants. Ca oxalate precipitation is not a stochastic process, suggesting the involvement of specific biochemical and cellular mechanisms. Microautoradiography of water lettuce (Pistia stratiotes) tissue exposed to 3H-glutamate showed incorporation into developing crystals, indicating potential acidic proteins associated with the crystals. Dissolution of crystals leaves behind a crystal-shaped matrix "ghost" that is capable of precipitation of Ca oxalate in the original crystal morphology. To assess whether this matrix has a protein component, purified crystals were isolated and analyzed for internal protein. Polyacrylamide gel electrophoresis revealed the presence of one major polypeptide of about 55 kD and two minor species of 60 and 63 kD. Amino acid analysis indicates the matrix protein is relatively high in acidic amino acids, a feature consistent with its solubility in formic acid but not at neutral pH. 45Ca-binding assays demonstrated the matrix protein has a strong affinity for Ca. Immunocytochemical localization using antibody raised to the isolated protein showed that the matrix protein is specific to crystal-forming cells. Within the vacuole, the surface and internal structures of two morphologically distinct Ca oxalate crystals, raphide and druse, were labeled by the antimatrix protein serum, as were the surfaces of isolated crystals. These results demonstrate that a specific Ca-binding protein exists as an integral component of Ca oxalate crystals, which holds important implications with respect to regulation of crystal formation. PMID:14555781

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  13. 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

  14. 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

  15. 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...

  16. 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...

  17. Heat regeneration in Malone-type liquid engines using a parallel-plate thermodynamic pile geometry

    NASA Astrophysics Data System (ADS)

    Allen, P. C.; Fisher, G. H.; Knight, W. R.; Paulson, D. N.; Wheatley, J. C.

    1981-06-01

    Liquids working in heat engines require especially effective thermal regeneration as they flow between the remote and ambient temperature regions of a machine. Using liquid Freon 114 (C2Cl2F4) as a test fluid, we have studied this process experimentally in a parallel-plate geometry for the pulsating unidirectional flow of a Malone engine. A theoretical analysis of the thermohydrodynamical process is presented whose results compare favorably with experiment. For a constant average volume rate of flow of liquid, the regenerative loss decreases as the period of the engine decreases.

  18. Heat regeneration in Malone-type liquid engines using a parallel-plate thermodynamic pile geometry

    SciTech Connect

    Allen, P.C.; Fisher, G.H.; Knight, W.R.; Paulson, D.N.; Wheatley, J.C.

    1981-06-01

    Liquids working in heat engines require especially effective thermal regeneration as they flow between the remote and ambient temperature regions of a machine. Using liquid Freon 114 (C/sub 2/Cl/sub 2/F/sub 4/) as a test fluid, we have studied this process experimentally in a parallel-plate geometry for the pulsating unidirectional flow of a Malone engine. A theoretical analysis of the thermohydrodynamical process is presented whose results compare favorably with experiment. For a constant average volume rate of flow of liquid, the regenerative loss decreases as the period of the engine decreases.

  19. The role of the Malone antegrade continence enema (MACE) in the management of myelodeysplatic patients.

    PubMed

    Zamilpa, Ismael; Koyle, Martin A

    2009-01-01

    Myelodysplasia is a congenital neural tube defect commonly affecting bladder and bowel function. Management of fecal incontinence is paramount to achieve patient independence and self-confidence. When conservative measures fail alternative invasive methods can be successfully applied. The Malone antegrade continence enema (MACE) was introduced in the late 1980's to treat spina bifida patients with fecal incontinence refractory to conservative management. Since its introduction, multiple successful variations have been described and its role has expanded. Indeed, the MACE has revolutionized the care of myelodysplastic patients, their bowel function, and ultimately their self image. PMID:21791795

  20. Oxalobacter formigenes Colonization and Oxalate Dynamics in a Mouse Model.

    PubMed

    Li, Xingsheng; Ellis, Melissa L; Knight, John

    2015-08-01

    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

  1. 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

  2. Cannabinoid CB2 receptor agonists protect the striatum against malonate toxicity: relevance for Huntington’s disease

    PubMed Central

    Sagredo, Onintza; González, Sara; Aroyo, Ilia; Pazos, María Ruth; Benito, Cristina; Lastres-Becker, Isabel; Romero, Juan P.; Tolón, Rosa M.; Mechoulam, Raphael; Brouillet, Emmanuel; Romero, Julián; Fernández-Ruiz, Javier

    2009-01-01

    Cannabinoid agonists might serve as neuroprotective agents in neurodegenerative disorders. Here, we examined this hypothesis in a rat model of Huntington’s disease (HD) generated by intrastriatal injection of the mitochondrial complex II inhibitor malonate. Our results showed that only compounds able to activate CB2 receptors were capable of protecting striatal projection neurons from malonate-induced death. That CB2 receptor agonists are neuroprotective was confirmed by using the selective CB2 receptor antagonist, SR144528, and by the observation that mice deficient in CB2 receptor were more sensitive to malonate than wild-type animals. CB2 receptors are scarce in the striatum in healthy conditions but they are markedly up-regulated after the lesion with malonate. Studies of double immunostaining revealed a significant presence of CB2 receptors in cells labelled with the marker of reactive microglia OX-42, and also in cells labelled with GFAP (a marker of astrocytes). We further showed that the activation of CB2 receptors significantly reduced the levels of tumor necrosis factor-α (TNF-α) that had been increased by the lesion with malonate. In summary, our results demonstrate that stimulation of CB2 receptors protect the striatum against malonate toxicity, likely through a mechanism involving glial cells, in particular reactive microglial cells in which CB2 receptors would be up-regulated in response to the lesion. Activation of these receptors would reduce the generation of proinflammatory molecules like TNF-α. Altogether our results support the hypothesis that CB2 receptors could constitute a therapeutic target to slowdown neurodegeneration in HD. PMID:19115380

  3. Malonic Semialdehyde Reductase from the Archaeon Nitrosopumilus maritimus Is Involved in the Autotrophic 3-Hydroxypropionate/4-Hydroxybutyrate Cycle

    PubMed Central

    Otte, Julia; Mall, Achim; Schubert, Daniel M.; Könneke, Martin

    2014-01-01

    The recently described ammonia-oxidizing archaea of the phylum Thaumarchaeota are highly abundant in marine, geothermal, and terrestrial environments. All characterized representatives of this phylum are aerobic chemolithoautotrophic ammonia oxidizers assimilating inorganic carbon via a recently described thaumarchaeal version of the 3-hydroxypropionate/4-hydroxybutyrate cycle. Although some genes coding for the enzymes of this cycle have been identified in the genomes of Thaumarchaeota, many other genes of the cycle are not homologous to the characterized enzymes from other species and can therefore not be identified bioinformatically. Here we report the identification and characterization of malonic semialdehyde reductase Nmar_1110 in the cultured marine thaumarchaeon Nitrosopumilus maritimus. This enzyme, which catalyzes the reduction of malonic semialdehyde with NAD(P)H to 3-hydroxypropionate, belongs to the family of iron-containing alcohol dehydrogenases and is not homologous to malonic semialdehyde reductases from Chloroflexus aurantiacus and Metallosphaera sedula. It is highly specific to malonic semialdehyde (Km, 0.11 mM; Vmax, 86.9 μmol min−1 mg−1 of protein) and exhibits only low activity with succinic semialdehyde (Km, 4.26 mM; Vmax, 18.5 μmol min−1 mg−1 of protein). Homologues of N. maritimus malonic semialdehyde reductase can be found in the genomes of all Thaumarchaeota sequenced so far and form a well-defined cluster in the phylogenetic tree of iron-containing alcohol dehydrogenases. We conclude that malonic semialdehyde reductase can be regarded as a characteristic enzyme for the thaumarchaeal version of the 3-hydroxypropionate/4-hydroxybutyrate cycle. PMID:25548047

  4. 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

  5. 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

  6. Calcium oxalate crystals in eucalypt ectomycorrhizae: morphochemical characterization.

    PubMed

    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

  7. 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

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

    NASA Astrophysics Data System (ADS)

    Laongsri, Bunthoon; Harrison, Roy M.

    2013-06-01

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

  9. Enhanced photochemical decomposition of environmentally persistent perfluorooctanoate by coexisting ferric ion and oxalate.

    PubMed

    Wang, Yuan; Zhang, Pengyi

    2016-05-01

    Perfluorooctanoic acid (PFOA), an environmentally persistent pollutant, was found to be quickly decomposed under 254 nm UV irradiation in the presence of ferric ion and oxalic acid. To understand the PFOA decomposition mechanism by this process, the effects of reaction atmosphere and concentrations of ferric ions and oxalic acids on PFOA decomposition were investigated, as well as decomposition intermediates. PFOA mainly decomposes via two pathways: (i) photochemical oxidation via Fe(III)-PFOA complexes and (ii) one-electron reduction caused by carboxylate anion radical (CO2 (•-)), which was generated by photolysis of ferrioxalate complexes. Under excess oxalic acid, PFOA decomposition was accelerated, and its corresponding half-life was shortened from 114 to 34 min as ferric concentration increased from 7 to 80 μM. Besides fluoride ions, six shorter chain perfluorinated carboxylic acids (PFCAs) bearing C2-C7 were identified as main intermediates. The presence of O2 promoted the redox recycling of Fe(3+)/Fe(2+) and thus avoided the exhaustion of the Fe(III). PMID:26846242

  10. 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

  11. Oligomeric proanthocyanidins protect against HK-2 cell injury induced by oxalate and calcium oxalate monohydrate crystals.

    PubMed

    Wang, Shuo; Du, Peng; Zhang, Ning; Liu, Jia; Tang, Xingxing; Zhao, Qiang; Yang, Yong

    2016-06-01

    The purpose of the study was to test whether the antioxidants oligomeric proanthocyanidins (OPCs) could provide protection against oxalate and calcium oxalate monohydrate crystals (COM) toxicity in HK-2 cells. Four groups were chosen for the study: negative control group, positive control group (COM + oxalate), OPCs group (OPCs + COM + oxalate), Vit E group (Vit E + COM + oxalate). HK-2 cells were exposed for 4, 8, 12 and 24 h. The activity of HK-2 cell was assessed by MTT. Cellular injury was assessed by activity of Na(+)/K(+) ATP enzyme. Peroxidation level was assessed by malondialdehyde (MDA) content in medium and activity of superoxide dismutase (SOD). Morphological changes of HK-2 cell after exposed for 4 and 12 h in each group were observed under Transmission electron microscope (TEM). The effects of OPCs and VitE on oxalate- and COM-exposed cells were tested. After exposed to oxalate and COM crystals, activity of cells, Na(+)/K(+) ATP enzyme and SOD enzyme showed a significant reduction, and MDA content in medium was significantly increased. OPCs group: the addition of OPCs significantly increased activity of cell, SOD and Na(+)/K(+) ATP enzyme while MDA content was significantly decreased compared with the positive control group. VitE group: compared with the positive control group, activity of HK-2 cell, Na(+)/K(+) ATP enzyme was not significantly changed while SOD activity was restored, and MDA content was significantly decreased after the addition of Vit E. Morphological structure of HK-2 cell was extremely changed as observed under TEM after exposure to high level of COM crystals and oxalate. After the addition of OPCs or Vit E, amounts of cells with vacuoles formed in cytoplasms, karyotheca dissolved and nucleolus disappeared were less than in positive control group. The morphological structure changing in OPCs group was slighter than that in Vit E group. OPCs and vitamin E administration may prevent oxalate- and COM-mediated peroxidative

  12. 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…

  13. 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.

  14. 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.

  15. Optimized growth and characterization of cadmium oxalate single crystals in silica gel

    NASA Astrophysics Data System (ADS)

    Ezhil Raj, A. Moses; Jayanthi, D. Deva; Jothy, V. Bena

    2008-05-01

    Single crystals of cadmium oxalate hydrate have been grown in silica gel in the presence of divalent Cd 2+ ions impregnated with oxalic acid at room temperature. Gel aging technique was adopted to reduce the nucleation density and hence larger and more perfect single crystals were harvested. Obtained crystals exhibit triclinic structure with unit cell dimensions a = 6.0059 Å, b = 6.66 Å, c = 8.49 Å, α = 105.71°, β = 98.99° and γ = 74.66°. IR spectrum indicates the presence of oxalate ligands and water of crystallization. Thermal behavior and stability of the grown cadmium oxalate crystals were investigated in the temperature range of 30-600 °C. A.C. electrical conductivity of Cd(C 2O 4)·3H 2O was measured for different frequencies and was found to lie between usual conductivities of semiconductor and insulator. The activation energy required to move permanent intrinsic defects in the crystal lattice was found and was equal to 0.15 eV.

  16. 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

  17. Antilithic effects of extracts from Urtica dentata hand on calcium oxalate urinary stones in rats.

    PubMed

    Xiang, Ming; Zhang, Shasha; Lu, Jingli; Li, Lulu; Hou, Wenrui; Xie, Mingxing; Zeng, Ying

    2011-10-01

    This study examined the potential antilithic effects of a traditional Chinese medicine Urtica dentata Hand (UDH) in experimental rats and screened the optimal extract of UDH as a possible therapeutic agent for kidney stones. The rat model of urinary calcium oxalate stones was induced by intragastric (i.g.) administration of 2 mL of 1.25% ethylene glycol (EG) and 1% ammonium chloride (AC) for 28 days and was confirmed by Color Doppler ultrasound imaging. The rats in different experimental groups were then intragastrically given petroleum ether extract (PEE), N-butanol extract (NBE), aqueous extract (AqE) of UDH, Jieshitong (positive control drug), and saline, respectively. Treatment with NBE significantly reduced the elevated levels of urinary calcium, uric acid, phosphate, as well as increased urinary output. Accordingly, the increased calcium, oxalate levels and the number of calcium oxalate crystals deposits were remarkably reverted in the renal tissue of NBE-treated rats. In addition, NBE also prevented the impairment of renal function to decrease the contents of blood urea nitrogen (BUN) and creatinine. Taken together, these data suggest that NBE of UDH has a beneficial effect on calcium oxalate urinary stones in rats by flushing the stones out and protecting renal function. PMID:22038359

  18. Aircraft measurement of dicarboxylic acids in the free tropospheric aerosols over the western to central North Pacific

    NASA Astrophysics Data System (ADS)

    Narukawa, M.; Kawamura, K.; Okada, K.; Zaizen, Y.; Makino, Y.

    2003-07-01

    Aircraft observation of aerosols was conducted in February 2000, for spatial and vertical distributions of dicarboxylic acids in the free troposphere over the western to central North Pacific. Oxalic, malonic, adipic and azelaic acids were detected in the aerosol samples as the major species. Concentrations of these diacids decreased exponentially with an increase in altitude. They were higher in the western North Pacific (130°E) and decrease eastward. Local flights conducted over Naha (Okinawa), Iwo-jima and Saipan showed that diacid concentrations decreased from the lower to upper troposphere. In the atmosphere over Saipan, where the air is not strongly affected from polluted East Asia, diacid concentrations were almost below the detection limit. Vertical profiles of diacids over Naha and Iwo-jima would be typical over the western North Pacific during winter, suggesting that diacids were significantly injected to the free troposphere from East Asia. Backward air mass trajectories also suggested that the diacids in the free troposphere over the North Pacific are strongly affected by the outflow from East Asia. Diacids, which were produced by both primary emission and secondary photochemical processes in polluted air of East Asia, could alter the physico-chemical properties of aerosols in the free troposphere over the western North Pacific.

  19. Reactive uptake of N2O5 by aerosols containing dicarboxylic acids. Effect of particle phase, composition, and nitrate content.

    PubMed

    Griffiths, Paul T; Badger, Claire L; Cox, R Anthony; Folkers, Mareike; Henk, Hartmut H; Mentel, Thomas F

    2009-04-30

    Reactive uptake coefficients for loss of N(2)O(5) to micron-size aerosols containing oxalic malonic, succinic, and glutaric acids, and mixtures with ammonium hydrogen sulfate and ammonium sulfate, are presented. The uptake measurements were made using two different systems: atmospheric pressure laminar flow tube reactor (Cambridge) and the Large Indoor Aerosol Chamber at Forschungszentrum Juelich. Generally good agreement is observed for the data recorded using the two techniques. Measured uptake coefficients lie in the range 5 x 10(-4)-3 x 10(-2), dependent on relative humidity, on particle phase, and on particle composition. Uptake to solid particles is generally slow, with observed uptake coefficients less than 1 x 10(-3), while uptake to liquid particles is around an order of magnitude more efficient. These results are rationalized using a numerical model employing explicit treatment of both transport and chemistry. Our results indicate a modest effect of the dicarboxylic acids on uptake and confirm the strong effect of particle phase, liquid water content, and particulate nitrate concentrations. PMID:19385680

  20. Improving nutritional quality and fungal tolerance in soya bean and grass pea by expressing an oxalate decarboxylase.

    PubMed

    Kumar, Vinay; Chattopadhyay, Arnab; Ghosh, Sumit; Irfan, Mohammad; Chakraborty, Niranjan; Chakraborty, Subhra; Datta, Asis

    2016-06-01

    Soya bean (Glycine max) and grass pea (Lathyrus sativus) seeds are important sources of dietary proteins; however, they also contain antinutritional metabolite oxalic acid (OA). Excess dietary intake of OA leads to nephrolithiasis due to the formation of calcium oxalate crystals in kidneys. Besides, OA is also a known precursor of β-N-oxalyl-L-α,β-diaminopropionic acid (β-ODAP), a neurotoxin found in grass pea. Here, we report the reduction in OA level in soya bean (up to 73%) and grass pea (up to 75%) seeds by constitutive and/or seed-specific expression of an oxalate-degrading enzyme, oxalate decarboxylase (FvOXDC) of Flammulina velutipes. In addition, β-ODAP level of grass pea seeds was also reduced up to 73%. Reduced OA content was interrelated with the associated increase in seeds micronutrients such as calcium, iron and zinc. Moreover, constitutive expression of FvOXDC led to improved tolerance to the fungal pathogen Sclerotinia sclerotiorum that requires OA during host colonization. Importantly, FvOXDC-expressing soya bean and grass pea plants were similar to the wild type with respect to the morphology and photosynthetic rates, and seed protein pool remained unaltered as revealed by the comparative proteomic analysis. Taken together, these results demonstrated improved seed quality and tolerance to the fungal pathogen in two important legume crops, by the expression of an oxalate-degrading enzyme. PMID:26798990

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. Structural Insights into an Oxalate-producing Serine Hydrolase with an Unusual Oxyanion Hole and Additional Lyase Activity.

    PubMed

    Oh, Juntaek; Hwang, Ingyu; Rhee, Sangkee

    2016-07-15

    In Burkholderia species, the production of oxalate, an acidic molecule, is a key event for bacterial growth in the stationary phase. Oxalate plays a central role in maintaining environmental pH, which counteracts inevitable population-collapsing alkaline toxicity in amino acid-based culture medium. In the phytopathogen Burkholderia glumae, two enzymes are responsible for oxalate production. First, the enzyme oxalate biosynthetic component A (ObcA) catalyzes the formation of a tetrahedral C6-CoA adduct from the substrates acetyl-CoA and oxaloacetate. Then the ObcB enzyme liberates three products from the C6-CoA adduct: oxalate, acetoacetate, and CoA. Interestingly, these two stepwise reactions are catalyzed by a single bifunctional enzyme, Obc1, from Burkholderia thailandensis and Burkholderia pseudomallei Obc1 has an ObcA-like N-terminal domain and shows ObcB activity in its C-terminal domain despite no sequence homology with ObcB. We report the crystal structure of Obc1 in its apo and glycerol-bound form at 2.5 Å and 2.8 Å resolution, respectively. The Obc1 N-terminal domain is essentially identical both in structure and function to that of ObcA. Its C-terminal domain has an α/β hydrolase fold that has a catalytic triad for oxalate production and a novel oxyanion hole distinct from the canonical HGGG motif in other α/β hydrolases. Functional analyses through mutagenesis studies suggested that His-934 is an additional catalytic acid/base for its lyase activity and liberates two additional products, acetoacetate and CoA. These results provide structural and functional insights into bacterial oxalogenesis and an example of divergent evolution of the α/β hydrolase fold, which has both hydrolase and lyase activity. PMID:27226606

  6. 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.

  7. Effect of Room Temperature Ionic Liquid on the Formation of the Complex Oxalate-Sodium Morin-5-Sulfonate-Aluminium(III): Application to the Fluorescence Determination of Oxalate Ion.

    PubMed

    Nizar, Syaza Atikah; Mohd Suah, Faiz Bukhari

    2016-07-01

    The effect of room temperature ionic liquid (RTIL) on the formation of the fluorescence ternary complex oxalate-sodium morin-5-sulfonate (NaMSA)-Aluminium(III) has been studied. In weakly acidic medium and in the presence of RTIL, 1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6), total complex formation is achieved as compared with the formation of the binary complex of NaMSA-Aluminium(III). The fluorescence characteristics of the system allowed the establishment of a very sensitive method for the spectrofluorimetric determination of oxalate ion. The ternary complex formed its highest fluorescence signal at 513 nm and excitation at 420 nm. In these conditions, the method produces a detection limit of 0.57 ng mL(-1). The procedure has been satisfactorily applied to the determination of oxalate ion in a vegetal tissue (spinach leaves). PMID:27286697

  8. 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

  9. Stereochemical evaluation of bis(phosphine) copper catalysts for the asymmetric alkylation of 3-bromooxindoles with α-arylated malonate esters

    PubMed Central

    Lee, Chung Whan; Han, Seo-Jung; Virgil, Scott C.; Stoltz, Brian M.

    2014-01-01

    An improved method for the asymetric alkylation of 3-bromooxindoles with α-arylated malonate esters is described. The asymmetric alkylation demonstrated was achieved up to 70% ee utilizing a copper(II) bis(phosphine) complex. PMID:25983348

  10. 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

  11. 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.

  12. 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…

  13. 21 CFR 862.1542 - Oxalate test system.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Oxalate test system. 862.1542 Section 862.1542 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test Systems § 862.1542 Oxalate test system. (a) Identification....

  14. 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 ...

  15. 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.

  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. PMID:25816022

  18. Formation of Hexacoordinate Mn(III) in Bacillus subtilis Oxalate Decarboxylase Requires Catalytic Turnover.

    PubMed

    Zhu, Wen; Wilcoxen, Jarett; Britt, R David; Richards, Nigel G J

    2016-01-26

    Oxalate decarboxylase (OxDC) catalyzes the disproportionation of oxalic acid monoanion into CO2 and formate. The enzyme has long been hypothesized to utilize dioxygen to form mononuclear Mn(III) or Mn(IV) in the catalytic site during turnover. Recombinant OxDC, however, contains only tightly bound Mn(II), and direct spectroscopic detection of the metal in higher oxidation states under optimal catalytic conditions (pH 4.2) has not yet been reported. Using parallel mode electron paramagnetic resonance spectroscopy, we now show that substantial amounts of Mn(III) are indeed formed in OxDC, but only in the presence of oxalate and dioxygen under acidic conditions. These observations provide the first direct support for proposals in which Mn(III) removes an electron from the substrate to yield a radical intermediate in which the barrier to C-C bond cleavage is significantly decreased. Thus, OxDC joins a small list of enzymes capable of stabilizing and controlling the reactivity of the powerful oxidizing species Mn(III). PMID:26744902

  19. Regioselective carboannulation of electron-deficient allenes with dialkyl (2-formylphenyl)malonates leading to multisubstituted naphthalenes.

    PubMed

    Koppanathi, Nagaraju; Swamy, K C Kumara

    2016-06-14

    An efficient base-catalysed regioselective carboannulation of allenoates (or allenylphosphonates) with dialkyl 2-(2-formylphenyl)malonates that leads to multi-substituted naphthalenes in high yields has been developed. This cascade reaction proceeds through Michael addition, cyclisation, dealkoxycarboxylation and tautomerisation. By using an allenylphosphine oxide, a species analogous to one of the intermediate species in the mechanistic pathway has been isolated. PMID:27180679

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. Kinetic and Spectroscopic Studies of Bicupin Oxalate Oxidase and Putative Active Site Mutants

    PubMed Central

    Moomaw, Ellen W.; Hoffer, Eric; Moussatche, Patricia; Salerno, John C.; Grant, Morgan; Immelman, Bridget; Uberto, Richard; Ozarowski, Andrew; Angerhofer, Alexander

    2013-01-01

    Ceriporiopsis subvermispora oxalate oxidase (CsOxOx) is the first bicupin enzyme identified that catalyzes manganese-dependent oxidation of oxalate. In previous work, we have shown that the dominant contribution to catalysis comes from the monoprotonated form of oxalate binding to a form of the enzyme in which an active site carboxylic acid residue must be unprotonated. CsOxOx shares greatest sequence homology with bicupin microbial oxalate decarboxylases (OxDC) and the 241-244DASN region of the N-terminal Mn binding domain of CsOxOx is analogous to the lid region of OxDC that has been shown to determine reaction specificity. We have prepared a series of CsOxOx mutants to probe this region and to identify the carboxylate residue implicated in catalysis. The pH profile of the D241A CsOxOx mutant suggests that the protonation state of aspartic acid 241 is mechanistically significant and that catalysis takes place at the N-terminal Mn binding site. The observation that the D241S CsOxOx mutation eliminates Mn binding to both the N- and C- terminal Mn binding sites suggests that both sites must be intact for Mn incorporation into either site. The introduction of a proton donor into the N-terminal Mn binding site (CsOxOx A242E mutant) does not affect reaction specificity. Mutation of conserved arginine residues further support that catalysis takes place at the N-terminal Mn binding site and that both sites must be intact for Mn incorporation into either site. PMID:23469254

  5. 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

  6. 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.

  7. Heterogeneous photodegradation of bisphenol A with iron oxides and oxalate in aqueous solution.

    PubMed

    Li, F B; Li, X Z; Li, X M; Liu, T X; Dong, J

    2007-07-15

    To understand the degradation of endocrine disrupting chemicals (EDCs) with existence of iron oxides and polycarboxylic acids in the natural environment, the photodegradation of bisphenol A (BPA) at the interface of iron oxides under UV illumination was conducted. Four iron oxides were prepared by a hydrothermal process and then sintered at different temperatures of 65, 280, 310, and 420 degrees C named "IO-65," "IO-280," "IO-310," and "IO-420," respectively. The prepared iron oxides were characterized by X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) methods. The XRD pattern of IO-65 showed a crystal structure of lepidocrocite (gamma-FeOOH) and that of IO-420 demonstrated a crystal structure of hematite (alpha-Fe(2)O(3)), while IO-280 and IO-310 have the mixed crystal structures of maghemite (gamma-Fe(2)O(3)) and hematite. The BET results revealed that the specific surface areas decreased with the increase of sintering temperature. The results demonstrated that the photodegradation of BPA depends strongly on the properties of iron oxides and oxalate, and pH. The properties of iron oxides influenced strongly the dependence of the BPA degradation on the oxalate concentration. The optimal initial concentrations of oxalate for BPA degradation under UV illumination were determined to be 2.0, 2.0, 2.4, and 2.0 mM for IO-65, IO-280, IO-310, and IO-420, respectively. The first-order kinetic constants k for BPA degradation under UV illumination in the presence of oxalate with the optimal initial concentration are ranked as IO-280>IO-310>IO-65>IO-420. The experiments demonstrated that the optimal pH value should be in the range of 3-4. Furthermore, the dependence of BPA degradation should be also attributable to the formation of the dissolved Fe-oxalate in the solution and the adsorbed Fe-oxalate on the surface of iron oxides, and also the formation of hydrogen peroxide. PMID:17451730

  8. Allyl­ammonium hydrogen oxalate hemihydrate

    PubMed Central

    Dziuk, Błażej; Zarychta, Bartosz; Ejsmont, Krzysztof

    2014-01-01

    In the title hydrated mol­ecular salt, C3H8N+·C2HO4 −·0.5H2O, the water O atom lies on a crystallographic twofold axis. The C=C—C—N torsion angle in the cation is 2.8 (3)° and the dihedral angle between the CO2 and CO2H planes in the anion is 1.0 (4)°. In the crystal, the hydrogen oxalate ions are linked by O—H⋯O hydrogen bonds, generating [010] chains. The allyl­ammonium cations bond to the chains through N—H⋯O and N—H⋯(O,O) hydrogen bonds. The water mol­ecule accepts two N—H⋯O hydrogen bonds and makes two O—H⋯O hydrogen bonds. Together, the hydrogen bonds generate (100) sheets. PMID:25249903

  9. Aluminum citrate prevents renal injury from calcium oxalate crystal deposition.

    PubMed

    Besenhofer, Lauren M; Cain, Marie C; Dunning, Cody; McMartin, Kenneth E

    2012-12-01

    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

  10. Heterogeneous photocatalytic reduction of chromium(VI) over TiO2 particles in the presence of oxalate: involvement of Cr(V) species.

    PubMed

    Testa, Juan J; Grela, María A; Litter, Marta I

    2004-03-01

    Cr(VI) photocatalytic reduction experiments over TiO2 particles under near UV irradiation in the presence of excess oxalate were performed at acid pH (2 and 3) and under air and N2 bubbling. Initial photonic efficiencies for Cr(VI) reduction are nearly the same under aerobic and anaerobic conditions, but show a significant increase at the lowest pH. At pH 2, the addition of oxalate facilitates Cr(VI) reduction, hindering the electron-shuttle mechanism taking place in pure water. The oxalate synergistic effect at pH 2 is lower than that previously found for EDTA and negligible at pH 3. Chromium(V) oxalate concentration profiles were obtained by EPR spectroscopy in the presence of excess oxalate at pH 1.5. Coordinated Cr(V) complexes [Cr(V)(O)(Ox)2]-, [Cr(V)(OH2)(Ox)2]-, and [Cr(V)(O)(OH)2(Ox)]- were identified, on the basis of the comparison of their corresponding g values with recent literature data. The kinetic analysis of the temporal evolution of the paramagnetic Cr(V) species indicates also an effective photocatalytic degradation of chromium(V) oxalate complexes. This new evidence reinforces previous findings regarding sequential one-electron-transfer processes in Cr(VI) photocatalytic reduction, suggesting that this route may represent a general behavior for the Cr(VI) reduction over UV-irradiated TiO2 particles. PMID:15046364

  11. 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.

  12. 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.

    1994-12-31

    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.

  13. A ferrous oxalate mediated photo-Fenton system: toward an increased biodegradability of indigo dyed wastewaters.

    PubMed

    Vedrenne, Michel; Vasquez-Medrano, Ruben; Prato-Garcia, Dorian; Frontana-Uribe, Bernardo A; Hernandez-Esparza, Margarita; de Andrés, Juan Manuel

    2012-12-01

    This study assessed the applicability of a ferrous oxalate mediated photo-Fenton pretreatment for indigo-dyed wastewaters as to produce a biodegradable enough effluent, likely of being derived to conventional biological processes. The photochemical treatment was performed with ferrous oxalate and hydrogen peroxide in a Compound Parabolic Concentrator (CPC) under batch operation conditions. The reaction was studied at natural pH conditions (5-6) with indigo concentrations in the range of 6.67-33.33 mg L(-1), using a fixed oxalate-to-iron mass ratio (C(2)O(4)(2-)/Fe(2+)=35) and assessing the system's biodegradability at low (257 mg L(-1)) and high (1280 mg L(-1)) H(2)O(2) concentrations. In order to seek the optimal conditions for the treatment of indigo dyed wastewaters, an experimental design consisting in a statistical surface response approach was carried out. This analysis revealed that the best removal efficiencies for Total Organic Carbon (TOC) were obtained for low peroxide doses. In general it was observed that after 20 kJ L(-1), almost every treated effluent increased its biodegradability from a BOD(5)/COD value of 0.4. This increase in the biodegradability was confirmed by the presence of short chain carboxylic acids as intermediate products and by the mineralization of organic nitrogen into nitrate. Finally, an overall decrease in the LC(50) for Artemia salina indicated a successful detoxification of the effluent. PMID:23142056

  14. 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.

  15. 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

  16. From dioxime oxalates to dihydropyrroles and phenanthridines via iminyl radicals.

    PubMed

    Portela-Cubillo, Fernando; Scanlan, Eoin M; Scott, Jackie S; Walton, John C

    2008-09-21

    Dioxime oxalates are useful precursors for the clean generation of iminyl radicals by sensitised UV photolysis and can be adapted for serviceable preparations of 3,4-dihydro-2H-pyrroles and phenanthridines. PMID:18802525

  17. 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

  18. Urine oxalate biological variation in patients with primary hyperoxaluria.

    PubMed

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

    2016-08-01

    Hyperoxaluria is a well-recognised risk factor for urolithiasis and patients with primary hyperoxaluria (PH) gradually build up calcium oxalate deposits leading to chronic kidney disease. Efforts to improve treatment for PH have focused on reducing urine oxalate excretion and thus decreasing lithogenesis. To determine the efficacy of treatments designed to alter a biochemical parameter it is necessary to know the biological and analytical variation of that parameter. In this study, we estimated the intra-individual biological variation of urine oxalate excretion in patients with PH, and from this determined what would constitute a significant change in the form of a reference change value (RCV). Each patient collected four 24-h urines on consecutive weeks. The intra-individual biological variation of oxalate excretion calculated from these samples ranged from 0 to 36 % with a mean of 14 %. The corresponding RCVs were 4-84 % with a mean of 32 %. This result implies that, on average, a reduction of almost one-third in urine oxalate excretion is required to prove an effect from treatment. The wide range of biological variation between individuals may reflect other, as yet unknown, determinants of oxaluria in PH, as well as inaccuracies in urine collection. The data suggest that it is more appropriate to use individual RCVs established prior to treatment to determine its efficacy: a relatively small fall in urine oxalate excretion may be outside the biological variation of some patients but not of others. PMID:26857252

  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. 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

  1. 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

  2. Composition and variation in vitamin C, carotenoids, protein, nitrate and oxalate contents in Celosia leaves.

    PubMed

    Prakash, D; Nath, P; Pal, M

    1995-04-01

    Twenty two lines/accessions belonging to 5 species of Celosia were analysed for their nutritional and antinutritional composition. The nutrient contents, vitamin C varied from 18.8 to 53.6 mg/100 g, carotenoids 9.1 to 15.1 mg/100g, protein 2.1 to 5.9%, while the antinutritional factors, nitrate 0.18 to 0.46% and oxalate 0.98 to 3.93%. Moisture ranged 81 to 89%. Variation of these parameters with leaf position and the amino acids profile of some promising lines was also evaluated. PMID:7659699

  3. 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

  4. A temperature dependent infrared absorption study of strong hydrogen bonds in bis(glycinium)oxalate

    NASA Astrophysics Data System (ADS)

    Bhatt, Himal; Deo, M. N.; Murli, C.; Vishwakarma, S. R.; Chitra, R.; Sharma, Surinder M.

    2016-05-01

    We report infrared absorption studies on Bis(glycinium)oxalate, an organic complex of the simplest amino acid Glycine, under varying temperatures in the range 77 - 350 K. The measurements have been carried out in the spectral range 400 - 4000 cm-1 and the strongest O-H---O hydrogen bond, which plays a vital role in the structural stabilization, has been studied. Subtle changes in widths of modes and temperature dependent frequency variations have been observed near 250 K. The hydrogen bonding network remains stable in the entire temperature range. This is in contrast to its reported high pressure behavior.

  5. 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

  6. Recovery of Am-Cm from high-activity waste concentrate by in-canyon-tank precipitation as oxalates

    SciTech Connect

    Gray, L W; Burney, G A; Wilson, T W; McKibben, J M

    1980-01-01

    Savannah River Laboratory and Savannah River Plant have been separating actinides for more than 25 years. Work continues to upgrade processes and to initiate new processes. This report summarizes work on a precipitation process to separate kg amounts of Am and Cm from hundreds of kilograms of NaNO/sub 3/ and Al(NO/sub 3/)/sub 3/. The developed process includes formic acid denitration of the Am-Cm bearing streams for acid adjustment; oxalate precipitation of the Am-Cm; and Mn/sup +2/ catalyzed oxidation of oxalate in both the decanted supernate and the precipitated actinides. The new process generates one fourth the radioactive waste as the solvent extraction process which it replaced, and produces a cleaner feed solution for downstream processing to separate the Am and Cm before conversion to their respective oxides.

  7. Complex pathogenesis of hyperoxaluria after jejunoileal bypass surgery. Oxalogenic substances in diet contribute to urinary oxalate.

    PubMed

    Hofmann, A F; Laker, M F; Dharmsathaphorn, K; Sherr, H P; Lorenzo, D

    1983-02-01

    Balance studies and oxalate loading tests were carried out in order to define the pathogenesis of hyperoxaluria in 8 patients with jejunoileal bypass surgery for severe obesity; two healthy volunteers were also studied. In the bypass patients, urinary oxalate was markedly elevated (118 +/- 43 mg/day, mean +/- SD) when they were on a high oxalate diet (252 mg/day). Hyperabsorption of dietary oxalate was confirmed by the markedly increased urinary recovery of [14C]oxalate given in a test meal. In addition, the oxalate radioactivity was excreted in urine far more slowly than in healthy volunteers, suggesting that the colon was a major site of oxalate absorption. Elevated urinary oxalate excretion persisted, averaging 38 +/- 12 mg/day, despite ingestion of a very low oxalate diet (approximately 6 mg/day), suggesting that the diet contained "oxalogenic" substances other than preformed dietary oxalate which also contributed to dietary oxalate in these patients. Urinary oxalate decreased in 7 of 8 patients, however, when protein-rich foods were removed from the diet, suggesting that at least one dietary factor was digestive products of protein or creatinine. These results confirm the current view that in patients with hyperoxaluria secondary to jejunoileal bypass, the majority of urinary oxalate derives from dietary oxalate that is absorbed from the colon. Tissue or bacterial production of oxalate or an oxalate precursor from dietary constituents associated with protein, however, also appears to contribute to urinary oxalate. The results provide an explanation for the reported difficulty of eliminating secondary hyperoxaluria by restriction of dietary oxalate alone. PMID:6848409

  8. Malonate in the nucleotide-binding site traps human AKAP18γ/δ in a novel conformational state.

    PubMed

    Bjerregaard-Andersen, Kaare; Østensen, Ellen; Scott, John D; Taskén, Kjetil; Morth, Jens Preben

    2016-08-01

    A-kinase anchoring proteins (AKAPs) are a family of proteins that provide spatiotemporal resolution of protein kinase A (PKA) phosphorylation. In the myocardium, PKA and AKAP18γ/δ are found in complex with sarcoendoplasmic reticulum Ca(2+)-ATPase 2 (SERCA2) and phospholamban (PLB). This macromolecular complex provides a means by which anchored PKA can dynamically regulate cytoplasmic Ca(2+) release and re-uptake. For this reason, AKAP18γ/δ presents an interesting drug target with therapeutic potential in cardiovascular disease. The crystal structure of the central domain of human AKAP18γ has been determined at the atomic resolution of 1.25 Å. This first structure of human AKAP18γ is trapped in a novel conformation by a malonate molecule bridging the important R-loop with the 2H phosphoesterase motif. Although the physiological substrate of AKAP18γ is currently unknown, a potential proton wire deep in the central binding crevice has been indentified, leading to bulk solvent below the R-loop. Malonate complexed with AKAP18γ at atomic resolution provides an excellent starting point for structure-guided drug design. PMID:27487922

  9. Methylmalonic semialdehyde dehydrogenase deficiency: demonstration of defective valine and beta-alanine metabolism and reduced malonic semialdehyde dehydrogenase activity in cultured fibroblasts

    SciTech Connect

    Gray, R.G.; Pollitt, R.J.; Webley, J.

    1987-08-01

    Intact cultured fibroblasts from a child with a new metabolic disorder, thought to be due to a deficiency of methylmalonic semialdehyde dehydrogenase, produced labeled CO/sub 2/ normally from (1-/sup 14/C)valine but not from (2-/sup 14/C)valine. CO/sub 2/ production from labeled beta-alanine was also much reduced, confirming the suspicion that malonic semialdehyde dehydrogenase is also deficient in this condition. An assay for malonic semialdehyde dehydrogenase in cell homogenates showed low activity but it was impossible to assess the degree of reduction.

  10. Oxalate-minus mutants of Sclerotinia sclerotiorum via T-DNA insertion accumulate fumarate in culture and retain pathogenicity on plants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sclerotinia sclerotiorum is a ubiquitous necrotrophic pathogen capable of infecting over 400 plant species including many economically important crops. Oxalic acid production has been shown in numerous studies to be a pathogenicity factor for S. sclerotiorum through several mechanisms. During our ra...

  11. 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

  12. [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

  13. Differentiation of Calcium Oxalate Monohydrate and Calcium Oxalate Dihydrate Stones Using Quantitative Morphological Information from Micro-Computerized and Clinical Computerized Tomography

    PubMed Central

    Duan, Xinhui; Qu, Mingliang; Wang, Jia; Trevathan, James; Vrtiska, Terri; Williams, James C.; Krambeck, Amy; Lieske, John; McCollough, Cynthia

    2014-01-01

    Purpose We differentiated calcium oxalate monohydrate and calcium oxalate dihydrate kidney stones using micro and clinical computerized tomography images. Materials and Methods A total of 22 calcium oxalate monohydrate and 15 calcium oxalate dihydrate human kidney stones were scanned using a commercial micro-computerized tomography scanner with a pixel size of 7 to 23 μm. Under an institutional review board approved protocol, image data on 10 calcium oxalate monohydrate and 9 calcium oxalate dihydrate stones greater than 5 mm were retrieved from a total of 80 patients who underwent clinical dual energy computerized tomography for clinical indications and had stones available for infrared spectroscopic compositional analysis. Micro and clinical computerized tomography images were processed using in-house software, which quantified stone surface morphology with curvature based calculations. A shape index was generated as a quantitative shape metric to differentiate calcium oxalate monohydrate from calcium oxalate dihydrate stones. Statistical tests were used to test the performance of the shape index. Results On micro-computerized tomography images the shape index of calcium oxalate monohydrate and calcium oxalate dihydrate stones significantly differed (ROC curve AUC 0.92, p <0.0001). At the optimal cutoff sensitivity was 0.93 and specificity was 0.91. On clinical computerized tomography images a significant morphological difference was also detected (p = 0.007). AUC, sensitivity and specificity were 0.90, 1 and 0.73, respectively. Conclusions On micro and clinical computerized tomography images a morphological difference was detectable in calcium oxalate monohydrate and calcium oxalate dihydrate stones larger than 5 mm. The shape index is a highly promising method that can distinguish calcium oxalate monohydrate and calcium oxalate dihydrate stones with reasonable accuracy. PMID:23142201

  14. Two-step oxalate approach for the preparation of high performance LiNi0.5Mn1.5O4 cathode material with high voltage

    NASA Astrophysics Data System (ADS)

    Liu, Zushan; Jiang, Yangmei; Zeng, Xiaoyuan; Xiao, Guan; Song, Huiyu; Liao, Shijun

    2014-02-01

    A high voltage cathode material, LiNi0.5Mn1.5O4, is synthesized with a two-step approach, in which the nickel-manganese oxalate precipitate is firstly obtained by adding oxalic acid to the solution of nickel and manganese ions precursors, followed by calcining the oxalates to obtain spinel nickel-manganese oxide, incorporating lithium ions with ball milling and calcining at 900 °C for 15 h. The materials are characterized with TG, XRD, SEM, BET and FTIR; it is revealed that both nickel-manganese oxide and final LiNi0.5Mn1.5O4 have well defined spinel structure. The LiNi0.5Mn1.5O4 spinel materials exhibit high capacities and good cyclic stability, the capacity of the materials is in the range from 126 to 136 mAh -1, depending on the calcining temperatures. The sample calcined at an optimal temperature of 900 °C exhibits best performance, the capacity is high up to 136 mAh g-1 at tenth cycle and the capacity retention after 50 cycles is 93%. For the sample prepared by mixing and milling oxalate with lithium salt, the discharge capacity is only 115 mAh g-1. We suggest that the spinel oxide derived from oxalate may play an important role for the high performance and high stability of the final cathode materials.

  15. Chemical transformations of CO2 in trifluoroacetic acid solutions

    NASA Astrophysics Data System (ADS)

    Vishnetskaya, M. V.; Ivanova, M. S.; Svichkarev, O. M.; Budynina, E. M.; Mel'nikov, M. Ya.

    2013-05-01

    It is established that a conversion reaction of carbon dioxide takes place at room temperature and atmospheric pressure in aqueous solutions of trifluoroacetic acid (TFA), which leads to the formation of oxalic acid and heavier polymerized products.

  16. 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.

  17. Seasonal and rainfall-type variations in inorganic ions and dicarboxylic acids and acidity of wet deposition samples collected from subtropical East Asia

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

    Rainfall samples were collected over a period of 3 years and 8 months in subtropical East Asia. They are categorized into different rainfall types and analyzed to assess the ionic composition and its effect on the acidity of wet deposition in southern Taiwan. Only 4% of samples had a pH of <5.0, indicating that the study area is not impacted significantly by acid rain. The volume-weighted mean (VWM) pH by rainfall type was Spring Rain 5.74, Typhoon Rain 5.56, Summer Rain 5.46, Typhoon Outer Circulation (TOC) Rain 5.45, Plum Rain 5.32 and Autumn-Winter Rain 5.29. Dilution effects were important to the equivalent ionic concentration of different rainfall types. HCO 3-, SO 42- and Cl - were detected as major anions whereas NH 4+, Na + and Ca 2+ were major cations. CO 2-derived HCO 3- was the major ionic species in all but Typhoon Rain and Spring Rain, in which the major species were Na + and Cl - and Ca 2+, respectively. Excluding HCO 3-, the major species were NH 4+, Na + and Ca 2+ in Plum Rain, the secondary photochemical products SO 42-, NO 3- and NH 4+ in TOC Rain and Summer Rain, and Na + and Ca 2+ in Autumn-Winter Rain. Calculation of arithmetic means showed that dicarboxylic acids contributed between 0.25% and 0.53% of the total ionic concentration and of these, oxalic acid contributed the least (81.3% of the dicarboxylic acid) to TOC Rain and the most (96.1% of the dicarboxylic acid) to Spring Rain, suggestive of long-range transport in the latter. Differences in wet deposition composition were shown to be a result of differences in local emissions and long-range transport (hence of prevailing wind direction) during the period of rainfall and of the frequency and volume of rain that typifies each rainfall type. Principal component analysis (PCA) further revealed that traffic-related and industrial organic and inorganic pollutants, their secondary photochemical products, sea salts, and dust are important contributors to wet deposition. Moreover, the ratio of

  18. 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

  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. 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.

  1. 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.

  2. Spin waves in antiferromagnetically coupled bimetallic oxalates.

    PubMed

    Reis, Peter L; Fishman, Randy S

    2009-01-01

    Bimetallic oxalates are molecule-based magnets with transition-metal ions M(II) and M(')(III) arranged on an open honeycomb lattice. Performing a Holstein-Primakoff expansion, we obtain the spin-wave spectrum of antiferromagnetically coupled bimetallic oxalates as a function of the crystal-field angular momentum L(2) and L(3) on the M(II) and M(')(III) sites. Our results are applied to the Fe(II)Mn(III), Ni(II)Mn(III) and V(II)V(III) bimetallic oxalates, where the spin-wave gap varies from 0 meV for quenched angular momentum to as high as 15 meV. The presence or absence of magnetic compensation appears to have no effect on the spin-wave gap. PMID:21817242

  3. 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

  4. Effective reduction in the nanoparticle sizes of NiO obtained via the pyrolysis of nickel malonate precursor modified using oleylamine surfactant

    NASA Astrophysics Data System (ADS)

    Lontio Fomekong, Roussin; Ngolui Lambi, John; Ebede, Guy Roland; Kenfack Tsobnang, Patrice; Tedjieukeng Kamta, Hypolite Mathias; Ngnintedem Yonti, Cedrik; Delcorte, Arnaud

    2016-09-01

    Nickel oxide nanoparticles were synthesized via thermal decomposition of two precursors, the first, a simple nickel malonate and the second, a nickel malonate modified by oleylamine, a surfactant, both having been synthesized by precipitation. While FTIR, TGA and ToF-SIMS were used to characterize the two precursors and to show the presence of oleylamine in the modified precursor, XRD, SEM, TEM and BET were employed to investigate the structure, the morphology and the specific surface area of the decomposition products obtained after pyrolysis. The results showed that the modification of nickel malonate by oleylamine was effective. The XRD results, which showed a cubic structure for the NiO obtained, suggest with SEM an important particle size reduction (at least 54%) when oleylamine was used to modify the nickel malonate precursor. The SEM images also showed a well-defined spherical nanoparticle morphology in both cases, not affected by the presence of oleylamine. The TEM also confirmed the reduction of particle size and their spherical nature but at the same time showed that, in the presence of oleylamine, there was no agglomeration resulting in a more uniform particle size distribution. The specific surface area of the NiO obtained by the oleylamine-modified precursor was 4.7 times larger than that obtained with the regular precursor. This again confirms the particle size reduction.

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

    PubMed

    Monje, Paula V; Baran, Enrique J

    2009-01-01

    Calcium oxalate druses were isolated from the stems and leaves of six Pereskioideae family members and investigated by infrared spectroscopy, showing that in all samples the biomineral was present in the form of whewellite, CaC2O4 x H2O. As Pereskia is thought to represent the "ancestral" condition of the leafless stem-succulent cacti, these results suggest that the biomineralization of calcium oxalate in Cactaceae represents a primitive characteristic of the group and also support a close genetic relationship between Pereskia and Opuntia. PMID:20158142

  6. 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

  7. 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

  8. Oxalate Nephropathy After Continuous Infusion of High-Dose Vitamin C as an Adjunct to Burn Resuscitation.

    PubMed

    Buehner, Michelle; 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

  9. Mixed anion (phosphate/oxalate) bonding to iron(III) materials.

    PubMed

    Kizewski, Fiona R; Boyle, Paul; Hesterberg, Dean; Martin, James D

    2010-02-24

    A novel phosphate/oxalate inorganic-organic hybrid material has been prepared to elucidate synthesis and bonding characteristics of iron(III) with both phosphate and organic matter (OM). Such mixed anion bonding of inorganic oxyanions and OM to iron(III) and aluminum(III) in environmental systems has been proposed but not proven, mainly because of the complexity of natural geochemical matrices. The compound reported here with the molecular formula of [C(3)H(12)N(2)](2)[Fe(5)(C(2)O(4))(2)(H(x)PO(4))(8)] (I) was hydrothermally synthesized and characterized by single crystal X-ray diffraction and X-ray absorption spectroscopy (XAS). In this new structure, Fe-O octahedra and P-O tetrahedra are connected by corner-sharing to form a 2-D network in the a-b plane. Oxalate anions cross-link these Fe-P layers constructing a 3-D anionic framework. A diprotonated structure-directing template, DAP (1,3-diaminopropane), resides in the oxalate layer of the structure and offsets the negative charge of the anionic framework. Iron K-edge XANES spectra confirmed that the iron in I is Fe(III). The crystal structure of I is used to successfully fit its Fe K-edge EXAFS spectrum, which exhibits spectral signatures that unambiguously identify iron-phosphate and iron-OM bonding. Such molecular spectroscopic features will be invaluable for the evaluation of complex environmental systems. Furthermore, syntheses demonstrated the critical role of the templating amine to mediate whether or not the iron(III) is reduced by the organic acid. PMID:20121236

  10. Mixed Anion (Phosphate/Oxalate) Bonding to Iron(III) Materials

    SciTech Connect

    Kizewski, F.; Boyle, P; Hesterberg, D; Martin, J

    2010-01-01

    A novel phosphate/oxalate inorganic-organic hybrid material has been prepared to elucidate synthesis and bonding characteristics of iron(III) with both phosphate and organic matter (OM). Such mixed anion bonding of inorganic oxyanions and OM to iron(III) and aluminum(III) in environmental systems has been proposed but not proven, mainly because of the complexity of natural geochemical matrices. The compound reported here with the molecular formula of [C{sub 3}H{sub 12}N{sub 2}]{sub 2}[Fe{sub 5}(C{sub 2}O{sub 4}){sub 2}(H{sub x}PO{sub 4}){sub 8}] (I) was hydrothermally synthesized and characterized by single crystal X-ray diffraction and X-ray absorption spectroscopy (XAS). In this new structure, Fe-O octahedra and P-O tetrahedra are connected by corner-sharing to form a 2-D network in the a-b plane. Oxalate anions cross-link these Fe-P layers constructing a 3-D anionic framework. A diprotonated structure-directing template, DAP (1,3-diaminopropane), resides in the oxalate layer of the structure and offsets the negative charge of the anionic framework. Iron K-edge XANES spectra confirmed that the iron in I is Fe(III). The crystal structure of I is used to successfully fit its Fe K-edge EXAFS spectrum, which exhibits spectral signatures that unambiguously identify iron-phosphate and iron-OM bonding. Such molecular spectroscopic features will be invaluable for the evaluation of complex environmental systems. Furthermore, syntheses demonstrated the critical role of the templating amine to mediate whether or not the iron(III) is reduced by the organic acid.

  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. 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.

  13. Electronic effects on keto-enol tautomerism of p-substituted aryl-1,3-diketone malonates

    NASA Astrophysics Data System (ADS)

    Jiménez-Cruz, Federico; Ríos-Olivares, Hector; García-Gutiérrez, José Luis; Mar, Lubanski Fragoza

    2015-12-01

    Electronic effects on keto-enol tautomerism of 1-(p-substituted aryl)-1,3-diketone malonates 1-10 were determined and established by NMR-Hammett linear free energy relationships. In addition, tautomeric equilibrium constants were determined for the title compounds by 1H NMR in DMSO-d6, showing an increasing to diketo tautomer with the increasing in the temperature. In this context, the enol form becomes less stable with increasing temperature suggesting that the intramolecular hydrogen bonding of the cis enol-keto form are increasingly broken at higher temperatures. In general, the enolic form (rather than the keto) is the most stable conformation due to its six member cyclic structure fulfilled by an internal O-H … O hydrogen bond.

  14. 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

  15. Production of battery grade materials via an oxalate method

    DOEpatents

    Belharouak, Ilias; Amine, Khalil

    2016-05-17

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

  16. 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.

  17. Acute Oxalate Nephropathy following Ingestion of Averrhoa bilimbi Juice.

    PubMed

    Nair, Sreeja; 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

  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. Biogenic and anthropogenic sources of oxalate in PM2.5 in a mega city, Shanghai

    NASA Astrophysics Data System (ADS)

    Yang, Fan; Gu, Zeping; Feng, Jialiang; Liu, Xiaohuan; Yao, Xiaohong

    2014-03-01

    In this study, thirty-seven 4-6 h PM2.5 samples were collected in both cold and warm seasons in 2006-2008 at an urban site in Shanghai (31°16‧47″N, 121°27‧15″E) for an investigation of the origins of oxalate. In the cold season, the oxalate from biomass burning accounted for 30 ± 11% (average ± standard deviation) of the observed oxalate using K+ as a tracer, while the oxalate oxidized from biogenic volatile organic species (BVOC) might be negligible because emissions of BVOC were only about 1/50 of volatile anthropogenic aromatics as reported in literature. The secondary oxalate (oxalate not from biomass burning) moderately correlated with sulfate and was more likely oxidized from anthropogenic aromatics. In the warm season, the oxalate from biomass burning accounted for 11 ± 8% of the observed oxalate. The low percentage was partially associated with the southeast wind while the open biomass burning occurred mainly in the northwest to the sampling site. In the warm-season samples containing low concentrations of sulfate, the secondary oxalate was also moderately correlated with sulfate. Further analysis showed that cloud (or fog) processed oxalate from biogenic precursors probably dominated the secondary oxalate in these samples. Higher concentrations of oxalate and higher ratio of oxalate to sulfate in the remaining warm-season samples than in cold-season samples also suggested that the oxalate derived from biogenic precursors was also likely an important contributor to the secondary oxalate.

  20. Oxalate secretion by ectomycorrhizal Paxillus involutus is mineral-specific and controls calcium weathering from minerals

    NASA Astrophysics Data System (ADS)

    Schmalenberger, A.; Duran, A. L.; Bray, A. W.; Bridge