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Sample records for ligand promoted dissolution

  1. Effects of anionic surfactants on ligand-promoted dissolution of iron and aluminum hydroxides.

    PubMed

    Carrasco, Naraya; Kretzschmar, Ruben; Pesch, Marie-Laure; Kraemer, Stephan M

    2008-05-15

    We investigated the influence of the surfactants sodium dodecyl sulfate (SDS) and rhamnolipid (RhL) on ligand-promoted dissolution of goethite (alpha-FeOOH) and boehmite (gamma-AlOOH) at pH 6. The siderophore desferrioxamine B (DFOB), its derivate desferrioxamine D (DFOD), ethylenediaminetetraacetic acid (EDTA), and 8-hydroxyquinoline-5-sulfonic acid (HQS) were used as ligands. The rates of ligand-promoted dissolution of goethite were significantly increased in the presence of low concentrations of anionic surfactants (<80 microM SDS; <6 mg/L RhL). At higher surfactant concentrations, however, the effects of surfactants were negligible. The dissolution rates in the presence of surfactants were not correlated with adsorbed amounts of ligands. Three possible factors contributing to these observations were further investigated and discussed: (i) adsorbed surfactants may influence ligand adsorption by changes in the ligand's surface speciation, (ii) re-adsorption of Fe-DFOB or Fe-DFOD complexes may lead to an underestimation of siderophore-promoted dissolution rates at high surfactant concentrations, and (iii) co-adsorption of protons to goethite with SDS may influence the dissolution rates. However, our results show that none of these three factors can satisfactorily explain the observed effects of anionic surfactants on ligand-promoted dissolution rates of iron and aluminum hydroxides.

  2. Oxalate adsorption at a plagioclase (An47) surface and models for ligand-promoted dissolution

    USGS Publications Warehouse

    Stillings, L.L.; Drever, J.I.; Poulson, S.R.

    1998-01-01

    Previous work on adsorption of oxalate at aluminosilicate surfaces suggests that maximum adsorption occurs through a bidentate attachment of the organic ligand, at near-neutral pH. Rates of ligand-promoted dissolution are expected to be greatest at this pH as well. We tested this model by measuring oxalate adsorption on the surface of andesine (An47), in solutions of pH 3- 5 and total oxalate concentrations of 0-8 mM. Contrary to expectation, the greatest adsorption density of 24 ??mol m-2 total oxalate was observed at pH 3 and 8 mM total oxalate. Adsorption is dependent upon the activities of both oxalate (C2O42-) and bioxalate (HC2O4-) in solution and can be modeled with either a two-term Langmuir or a two-term Freundlich isotherm. A Freundlich adsorption model provided the best fit to rate data because it was not constrained to a finite number of adsorption sites, as was the Langmuir model. The two-term ligand adsorption model was incorporated into a rate model: R(tot) = k(H-)[H(ads)/+](L) + k(HOx-)[HOx(ads)/-] + k(Ox2- )[Ox2(ads)/-] where R(tot) is the net dissolution rate of the feldspar, [i(ads)] is the concentration of species i adsorbed to the surface, and k(i) is the rate constant for release of the surface complex. The model was fit to data for oxalate-promoted dissolution of andesine, resulting in estimates for the rate constants of k(HOx-) = 1.16 x 10-12, k(Ox2-) = 1.05 x 10-12, and k(H-) = 9.61 x 10-13 mol of feldspar (??mol of i) (??mol of i)-1 s-1.Previous work on adsorption of oxalate at aluminosilicate surfaces suggests that maximum adsorption occurs through a bidentate attachment of the organic ligand, at near-neutral pH. Rates of ligand-promoted dissolution are expected to be greatest at this pH as well. We tested this model by measuring oxalate adsorption on the surface of andesine (An47), in solutions of pH 3-5 and total oxalate concentrations of 0-8 mM. Contrary to expectation, the greatest adsorption density of 24 ??mol m-2 total oxalate was

  3. Examination of Uranium(VI) Leaching During Ligand Promoted Dissolution of Waste Tank Sludge Surrogates

    SciTech Connect

    Powell, Brian; Powell, Brian A.; Rao, Linfeng; Nash, Kenneth. L.

    2008-06-10

    The dissolution of synthetic boehmite (?-AlOOH) by 1-hydroxyethane-1,1-diphosphonic acid (HEDPA) was examined in a series of batch adsorption/dissolution experiments. Additionally, the leaching behavior of {sup 233}U(VI) from boehmite was examined as a function of pH and HEDPA concentration. The results are discussed in terms of sludge washing procedures that may be utilized during underground tank waste remediation. In the pH range 4 to 10, complexation of Al(III) by HEDPA significantly enhanced dissolution of boehmite. This phenomenon was especially pronounced in the neutral pH region where the solubility of aluminum, in the absence of complexants, is limited by the formation of sparsely soluble aluminum hydroxides. At pH higher than 10, dissolution of synthetic boehmite was inhibited by HEDPA, likely due to sorption of Al(III):HEDPA complexes. Addition of HEDPA to equilibrated U(VI)-synthetic boehmite suspensions yielded an increase in the aqueous phase uranium concentration. Partitioning of uranium between the solid and aqueous phase is described in terms of U(VI):HEDPA speciation and dissolution of the boehmite solid phase.

  4. Do organic ligands affect calcite dissolution rates?

    NASA Astrophysics Data System (ADS)

    Oelkers, Eric H.; Golubev, Sergey V.; Pokrovsky, Oleg S.; Bénézeth, Pascale

    2011-04-01

    Steady state Iceland-spar calcite dissolution rates were measured at 25 °C in aqueous solutions containing 0.1 M NaCl and up to 0.05 M dissolved bicarbonate at pH from 7.9 to 9.1 in the presence of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those most likely to be present in either (1) aquifers at the conditions pertinent to CO 2 sequestration or (2) soil/early diagenetic environments: acetate, phthalate, citrate, EDTA 4-, succinate, D-glucosaminate, L-glutamate, D-gluconate, 2,4-dihydroxybenzoate, 3,4-dihydroxybenzoate, fumarate, malonate, and gallate. Results show that the presence of <0.05 mol/kg of these organic anions changes calcite dissolution rates by less than a factor of 2.5 with the exception of citrate and EDTA 4-. The presence of 0.05 mol/kg citrate and EDTA 4- increases calcite dissolution rates by as much as a factor of 35 and 500, respectively, compared to rates in organic anion-free solutions. Further calcite dissolution experiments were performed in the presence of organic polymers similar to bacterial exudates, cell exopolysaccharides, and analogs of microbial cell envelopes: alginate, lichen extract, humic acid, pectin, and gum xanthan. In no case did the presence of <100 ppm of these organics change calcite dissolution rates by more than a factor of 2.5. Results obtained in this study suggest that the presence of aqueous organic anions negligibly affects calcite forward dissolution rates in most natural environments. Some effect on calcite reactivity may be observed, however, by the presence of organic anions if they change substantially the chemical affinity of the fluid with respect to calcite.

  5. Bacterial siderophores promote dissolution of UO2 under reducing conditions.

    PubMed

    Frazier, Scott W; Kretzschmar, Ruben; Kraemer, Stephan M

    2005-08-01

    Tetravalent actinides are often considered environmentally immobile due to their strong hydrolysis and formation of sparingly soluble oxide phases. However, biogenic ligands commonly found in the soil environment may increase their solubility and mobility. We studied the adsorption and dissolution kinetics of UO2 in the presence of a microbial siderophore, desferrioxamine-B (DFO-B), under reducing conditions. Using batch and continuous flow stirred tank reactors (CFSTR),we found that DFO-B increases the solubility of UIV and accelerates UO2 dissolution rates through a ligand-promoted dissolution mechanism. DFO-B adsorption to UO2 followed a Langmuir-type isotherm. The maximum adsorbed DFO-B concentrations were 3.3 micromol m(-2) between pH 3 and 8 and declined above pH 8. DFO-B dissolved UO2 at a DFO-B surface-saturated net rate of 64 nmol h(-1) m(-2) (pH 7.5, l = 0.01 M) according to the first-order rate equation R = kL[Lads], with a rate coefficient kL of 0.019 h(-1). Even at very low siderophore concentrations (e.g. 1 microM), net dissolution rates (16 nmol h(-1) m(-2), pH 7.5, l = 0.01 M) were substantially greater than net proton-promoted dissolution rates (3 nmol h(-1) m(-2), pH 7-7.5, l = 0.01 M). Interestingly, adding dissolved FeIII had negligible effects on DFO-B-promoted UO2 dissolution rates, despite its potential as a competitor for DFO-B and as an oxidant of UIV. Our results suggest that strong organic ligands could influence the environmental mobility of tetravalent actinides and should be considered in predictions for nuclear waste storage and remediation strategies. PMID:16124306

  6. Dissolution of Technetium(IV) Oxide by Natural and Synthetic Organic Ligands Under both Reducing and Oxidizing Conditions

    SciTech Connect

    Gu, Baohua; Dong, W.; Liang, Liyuan; Wall, Nathalie

    2011-01-01

    Technetium-99 (Tc) in nuclear waste is a significant environmental concern due to its long half-life and high mobility in the subsurface. Reductive precipitation of Tc(IV) oxides [TcO2(s)] is an effective means of immobilizing Tc, thereby impeding its migration in groundwater. However, TcO2(s) is subject to dissolution by oxidants and/or complexing agents. In this study we ascertain the effects of a synthetic organic ligand, ethylenediaminetetraacetate (EDTA), and two natural humic isolates on the dissolution and solubility of Tc(IV) oxides. Pure synthetic TcO2(s) (0.23 mM) was used in batch experiments to determine dissolution kinetics at pH ~6 under both reducing and oxidizing conditions. All organic ligands were found to enhance the dissolution of Tc(IV) oxides, increasing their solubility from ~10-8 M (without ligands) to 4 10-7 M under strictly anoxic conditions. Reduced Tc(IV) was also found to re-oxidize rapidly under oxic conditions, with an observed oxidative dissolution rate approximately an order of magnitude higher than that of ligand-promoted dissolution under reducing conditions. Significantly, oxidative dissolution was inhibited by EDTA but enhanced by humic acid compared with experiments without any complexing agents. The redox functional properties of humics, capable of facilitating intra-molecular electron transfer, may account for this increased oxidation rate under oxic conditions. Our results highlight the importance of complex interactions for the stability and mobility of Tc, and thus for the long-term fate of Tc in contaminated environments.

  7. Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part II: Siderophore-promoted dissolution

    NASA Astrophysics Data System (ADS)

    Mikutta, Christian; Kretzschmar, Ruben

    2008-02-01

    Ferrihydrite (Fh) coprecipitated with exopolymers of plants and microbes may differ in its geochemical reactivity from its abiotic counterpart. We synthesized Fh in the presence and absence of acid polysaccharides (polygalacturonic acid (PGA), alginate, xanthan) and characterized the physical and structural properties of the precipitates formed [Mikutta C., Mikutta R., Bonneville S., Wagner F., Voegelin A., Christl I. and Kretzschmar R. (2008) Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part I: Characterization. Geochim. Cosmochim. Acta]. In this paper, we focus on the reactivity of PGA and alginate coprecipitates and pure Fh, and studied their interaction with the microbial siderophore desferrioxamine B (DFOB) in the presence and absence of low molecular weight organic (LMWO) acid anions (malate, citrate). Batch adsorption and dissolution experiments were performed in the dark at pH 7 in 10 mM NaClO 4 background electrolyte. In the dissolution experiments, different modes of ligand addition were applied (single, simultaneous, stepwise). With an estimated Langmuir sorption maximum of 15 mmol/mol Fe, a PGA coprecipitate with 11% C org sorbed about four times as much DFOB as pure Fh, and the amount of DFOB sorbed was ˜4-fold larger than estimated from the sum of DFOB sorption to pure Fh and PGA alone. The apparent initial dissolution rates, Rapp-initial, and pseudo-first order rate coefficients, k, of the coprecipitates exceeded those of pure Fh by up to two orders of magnitude. Citrate and malate exerted a strong synergistic effect on the DFOB-promoted dissolution of pure Fh, whereas synergistic effects of both anions were absent or negligible for the coprecipitates. Rapp-initial of the citrate and DFOB-promoted dissolution of PGA coprecipitates increased with increasing molar C/Fe ratio of the coprecipitates, independent of the charge of the LMWO ligand. Our results indicate that polyuronates stabilize Fh particles sterically and /or

  8. Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

    NASA Astrophysics Data System (ADS)

    Pokrovsky, Oleg S.; Schott, Jacques; Castillo, Alain

    2005-02-01

    Brucite (Mg(OH) 2) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H 2PO 4- > catechol ≥ HCO 3- > ascorbate > citrate > oxalate > acetate ˜ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO 43-, CO 32-, F -, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO 42- and B(OH) 4- with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation. The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg

  9. Microbial exudate promoted dissolution and transformation of chromium containing minerals

    NASA Astrophysics Data System (ADS)

    Saad, E. M.; Sun, J.; Tang, Y.

    2015-12-01

    Because of its utility in many industrial processes, chromium has become the second most common metal contaminant in the United States. The two most common oxidation states of chromium in nature are Cr(III), which is highly immobile, and Cr(VI), which is highly mobile and toxic. In both natural and engineered environments, the most common remediation of Cr(VI) is through reduction, which results in chromium sequestration in the low solubility mixed Cr(III)-Fe(III) (oxy)hydroxide phases. Consequently, the stability of these minerals must be examined to assess the fate of chromium in the subsurface. We examined the dissolution of mixed Cr(III)-Fe(III) (oxy)hydroxides in the presence of common microbial exudates, including the siderophore desferrioxamine B (DFOB; a common organic ligand secreted by most microbes with high affinity for ferric iron and other trivalent metal ions) and oxalate (a common organic acid produced by microbes). The solids exhibited incongruent dissolution with preferential leaching of Fe from the solid phase. Over time, this leads to a more Cr rich mineral, which is known to be more soluble than the corresponding mixed mineral phase. We are currently investigating the structure of the reacted mineral phases and soluble Cr(III) species, as well as the potential oxidation and remobilization of the soluble Cr species. Results from this study will provide insights regarding the long term transport and fate of chromium in the natural environment in the presence of microbial activities.

  10. Simulating Succinate-Promoted Dissolution at Calcite {104} Steps

    NASA Astrophysics Data System (ADS)

    Mkhonto, D.; Sahai, N.

    2008-12-01

    Organic molecules of a wide range of molecular weights from small organic acids, amino-acids, acidic peptides and acidic proteins to humic and fulvic acids play a key role in modulating nucleation, crystal growth and dissolution of calcium carbonate polymorphs. In general, these acidic molecules inhibit calcite growth and, promote dissolution preferentially along specific crystallographic directions, in the process, regulating crystal shape and size, and even whether a metastable polymorph (e.g., vaterite or aragonite) is nucleated first. For example, chiral faces of calcite are selected by chiral amino-acids and the unusual {hk0} faces are expressed in the presence of amino-acids [Orme et al., 2001], and unusual heptagonal dissolution etch-pit are seen in the presence of succinate compared to the normal rhombohedral pits in water alone [Teng et al., 2006]. Thus, the presence of unusual crystal morphologies may indicate organic-mediated growth, thus serving as a biosignature. We have conducted the Molecular Dynamics (MD) simulations using the Consistent Valence Force Field (CVFF) as implemented in the FORCITE© module of the Materials Studio © software package (Accelrys, Inc. TM) to model the adsorption of succinate, a dicarboxylic acid, and charge- balancing Na+ ions on dry and hydrated steps in different directions on the {104} cleavage face of calcite [Mkhonto and Sahai, in prep.]. At the site of succinate adsorption, we find elongation of the interatomic distances (Ca-OCO3,i) between surface Ca2+ cation and the oxygen of the underlying inorganic CO32- anion the first surface layer of calcite, compared to the corresponding distances in the presence of water alone, suggesting greater ease of surface Ca2+ detachment. This result is consistent with the empirically observed increase in overall dissolution rate with succinate [Teng et al., 2006]. Furthermore, succinate adsorption lowers the step energies, which explains the appearance of steps in the unsusual [42

  11. Effect of pH and organic ligands on the kinetics of smectite dissolution at 25 °C

    NASA Astrophysics Data System (ADS)

    Golubev, Sergey V.; Bauer, Andreas; Pokrovsky, Oleg S.

    2006-09-01

    Forward dissolution rates of Na-Montmorillonite (Wyoming) SWy-2 smectite (Ca 0.06Na 0.56)[Al 3.08Fe(III) 0.38Mg 0.54] [Si 7.93 Al 0.07]O 20(OH) 4 were measured at 25 °C in a mixed-flow reactor equipped with interior dialysis compartment (6-8 kDa membrane) as a function of pH (1-12), dissolved carbonate (0.5-10 mM), phosphate (10 -5 to 0.03 M), and nine organic ligands (acetate, oxalate, citrate, EDTA, alginate, glucuronic acid, 3,4-dihydroxybenzoic acid, gluconate, and glucosamine) in the concentration range from 10 -5 to 0.03 M. In organic-free solutions, the Si-based rates decrease with increasing pH at 1 ⩽ pH ⩽ 8 with a slope close to -0.2. At 9 ⩽ pH ⩽ 12, the Si-based rates increase with a slope of ˜0.3. In contrast, non-stoichiometric Mg release weakly depends on pH at 1 ⩽ pH ⩽ 12 and decreases with increasing pH. The empirical expression describing Si-release rates [ R, mol/cm 2/s] obtained in the present study at 25 °C, I = 0.01 M is given by R=2.2·10-17·aH0.21+1.0·10-20+6·10-17·aOH0.33 At circum-neutral pH, the Si-release-based dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA > 3,4-DHBA > citrate ⩾ oxalate. Phosphate, glucuronate, glucosamine, gluconate, alginate, and acetate act as inhibitors of dissolution and HCO 3-, CO 32- exhibit no effect on dissolution rate. Non-stoichiometric, non-steady-state Mg release was very weakly affected by the presence of ligands. Analysis of reacted solid products using XRD, FT-IR, and XPS revealed no major change in structure, surface chemical composition or specific surface area as a function of pH, ligand concentration, and duration of experiments. Ligand-affected rates re-calculated to constant pH were interpreted using a phenomenological equation which postulates the Langmurian adsorption of a ligand on surface sites. Overall, results of this study demonstrate that very high concentrations (0.001-0.01 M) of organic ligands, whether they are

  12. Methanobactin-Promoted Dissolution of Cu-Substituted Borosilicate Glass

    NASA Astrophysics Data System (ADS)

    Kulczycki, E.; Fowle, D. A.; Knapp, C.; Graham, D. W.; Roberts, J. A.

    2006-12-01

    Mineral weathering processes play a major role in the global cycling of carbon and metals and there is an increasing realization that subsurface microbial activity may be a key factor regulating specific biogeochemical reactions and their rates. Methanobactin (mb) is an extracellular copper-binding compound excreted by methanotrophs who require copper to regulate methane oxidation. Cu that is available to the cell regulates the expression and activity of pMMO versus sMMO (particulate versus soluble methane monooxygenase, respectively), which are key enzymes responsible for methane oxidation. The primary focus of this study is to determine the effect of mb-promoted dissolution of Cu-substituted glass at low temperature and near neutral pH conditions, using batch dissolution experiments with and without the methanotroph, Methylonsinus trichosporium OB3b. Methanobactin promotes the weathering of Cu-substituted borosilicate glasses at rates faster than control experiments without methanobactin. Glasses with lower concentrations of copper (80 ppm) or no copper are dissolved more rapidly than those containing larger amounts of copper (800 ppm). Within the first 2 hours of reactivity, a greater quantity of mb appears to sorb onto the glass surface at higher copper concentrations and may limit mass transfer of Cu to solution. Furthermore gene expression in M. trichosporium OB3b, using real-time RT-PCR techniques, indicate that pmoA expression is influenced by mb in presence of Cu containing solid phases. These findings demonstrate that this methanotroph can directly access mineral-bound Cu and suggests that methane oxidation rates may be directly linked to mineral weathering in near-surface geologic settings.

  13. Siderophore-promoted dissolution of smectite by fluorescent Pseudomonas.

    PubMed

    Ferret, Claire; Sterckeman, Thibault; Cornu, Jean-Yves; Gangloff, Sophie; Schalk, Isabelle J; Geoffroy, Valérie A

    2014-10-01

    Siderophores are organic chelators produced by microorganisms to fulfil their iron requirements. Siderophore-promoted dissolution of iron-bearing minerals has been clearly documented for some siderophores, but few studies have addressed metabolizing siderophore-producing bacteria. We investigated iron acquisition from clays by fluorescent Pseudomonads, bacteria that are ubiquitous in the environment. We focused on the interactions between smectite and Pseudomonas aeruginosa, a bacterium producing two structurally different siderophores: pyoverdine and pyochelin. The presence of smectite in iron-limited growth media promoted planktonic growth of P. aeruginosa and biofilm surrounding the smectite aggregates. Chemical analysis of the culture media indicated increases in the dissolved silicon, iron and aluminium concentrations following smectite supplementation. The use of P. aeruginosa mutants unable to produce either one or both of the two siderophores indicated that pyoverdine, the siderophore with the higher affinity for iron, was involved in iron and aluminium solubilization by the wild-type strain. However, in the absence of pyoverdine, pyochelin was also able to solubilize iron but with a twofold lower efficiency. In conclusion, pyoverdine and pyochelin, two structurally different siderophores, can solubilize structural iron from smectite and thereby make it available for bacterial growth. PMID:25646536

  14. Silver nanoparticle dissolution in the presence of ligands and of hydrogen peroxide.

    PubMed

    Sigg, Laura; Lindauer, Ursula

    2015-11-01

    Dissolution of silver nanoparticles (AgNP with carbonate or citrate coating, total Ag 1-5 μM) was examined in the presence of the ligands cysteine, chloride and fulvic acids and of the oxidant hydrogen peroxide (H2O2) at low concentrations at pH 7.5. Dissolved Ag was separated from AgNP by ultrafiltration. Cysteine in the concentration range 0.2-5 μM resulted in an initial increase of dissolved Ag within few hours. Chloride (up to 0.1 mM) and fulvic acids (up to 15 mg L(-1)) had little effect on the dissolution of AgNP within hours to days. In contrast, very rapid dissolution within 1-2 h of both carbonate and citrate coated AgNP was observed in the presence of H2O2 in the concentration range 0.1-10 μM, under dark or light conditions. The high efficiency of H2O2 in dissolving AgNP is likely to be of importance in toxic effects of AgNP to algae, as H2O2 is produced and released into solution by algae. PMID:26310977

  15. Evidence for ligand hydrolysis and Fe(III) reduction in the dissolution of goethite by desferrioxamine-B

    NASA Astrophysics Data System (ADS)

    Simanova, Anna A.; Persson, Per; Loring, John S.

    2010-12-01

    Desferrioxamine-B (DFOB) is a bacterial trihydroxamate siderophore and probably the most studied to date. However, the manner in which DFOB adsorbs at mineral surfaces and promotes dissolution is still under discussion. Here we investigated the adsorption and dissolution reactions in the goethite-DFOB system using both in situ infrared spectroscopic and quantitative analytical methods. Experiments were carried out at a total DFOB concentration of 1 μmol/m 2, at pH 6, and in the absence of visible light. Our infrared spectroscopic results indicated that the adsorption of DFOB was nearly complete after a 4-h reaction time. In an attempt to determine the coordination mode at the goethite surface, we compared the spectrum of adsorbed DFOB after a 4-h reaction time to the spectra of model aqueous species. However, this approach proved too simplistic in the case of such a complex ligand as DFOB, and we suggest that a more detailed investigation (IR in D 2O, EXAFS of adsorbed model complexes) is needed to elucidate the structure of the adsorbed siderophore. Between a 4-h and 4-day reaction time, we observed the growth of carboxylate stretching bands at 1548 and 1404 cm -1, which are indicators of DFOB hydrolysis. Acetate, a product of DFOB hydrolysis at its terminal hydroxamate group, was quantified by ion chromatography. Its rate of formation was linear and nearly the same as the rate of Fe(III) dissolution. The larger hydrolysis product, a hydroxylamine fragment, was not detected by LC-MS. However, a signal due to the oxidized form of this fragment, a nitroso compound, was found to increase linearly with time, which is an indirect indication for Fe(III) reduction. Based on these findings, we propose that DFOB undergoes metal-enhanced hydrolysis at the mineral surface followed by the reduction of surface Fe(III). While Fe(II) was not detected in solution, this is likely because it remains adsorbed at the goethite surface or becomes buried in the goethite crystal by

  16. Dissolution of Uranium-Bearing Minerals and Mobilization of Uranium by Organic Ligands in a Biologically Reduced Sediment

    SciTech Connect

    Luo, Wensui; Gu, Baohua

    2011-01-01

    The stability and mobility of uranium (U) is a concern following its reductive precipitation or immobilization by techniques such as bioremediation at contaminated sites. In this study, the influences of complexing organic ligands such as citrate and ethylenediaminetetraacetate (EDTA) on the mobilization of U were investigated in both batch and column flow systems using a contaminated and bioreduced sediment. Results indicate that both reduced U(IV) and oxidized U(VI) in the sediment can be effectively mobilized with the addition of EDTA or citrate under anaerobic conditions. The dissolution and mobilization of U appear to be correlated to the dissolution of iron (Fe)- or aluminum (Al)-bearing minerals, with EDTA being more effective (with R2 0.89) than citrate (R2 <0.60) in dissolving these minerals. The column flow experiments confirm that U, Fe, and Al can be mobilized by these ligands under anoxic conditions, although the cumulative amounts of U removal constituted ~0.1% of total U present in this sediment following a limited period of leaching. This study concludes that the presence of complexing organic ligands may pose a long-term concern by slowly dissolving U-bearing minerals and mobilizing U even under a strict anaerobic environment.

  17. Dissolution of barite by a chelating ligand: An atomic force microscopy study

    NASA Astrophysics Data System (ADS)

    Putnis, Andrew; Junta-Rosso, Jodi L.; Hochella, Michael F., Jr.

    1995-11-01

    Atomic Force Microscopy (AFM) has been used to observe the dissolution of (001) cleavage surfaces of barite (BaSO 4) in deionized water and in solutions of DTPA (diethylene triamine pentaacetic acid), a synthetic metal-ion chelating agent. Experiments were carried out in situ in a fluid cell as well as in air on samples previously etched and dried. In water the principal dissolution features are etch pits bound by {210} faces. In DTPA, there is a different dissolution process which on an (001) surface results in the removal of layers that are half-unit cell thick (3.5 Å). Etch pits within each half-layer are bound by {110} and {100} faces and occur in two different orientations which are related by a 2 1 screw axis parallel to the c crystallographic axis. Only one pit orientation is found within each half-layer, and this orientation is determined by the position of the surface sulfate groups. The etch pit geometry suggests that the active ends of a DTPA molecule form bonds to Ba 2+ ions along [110] directions. Two concentrations of DTPA solutions were studied, 0.05 and 0.5 M. These concentrations are used in the development of commercial solvents for barite scale deposits in oil wells. In these experiments the 0.05 M DTPA solution was found to be considerably more reactive as a solvent than the more concentrated solution, suggesting that surface passivation of the barite occurs at high DTPA concentrations.

  18. Siderophore Promoted Dissolution of a Series of Mn-Substituted Goethites

    NASA Astrophysics Data System (ADS)

    Holmstrom, S. J.; Sposito, G.

    2005-12-01

    The presence of organic ligands, like siderophores, can strongly influence mineral dissolution. Recent research suggests that at least some siderophores enhance mineral dissolution by formation of surface complexes with Fe and Mn. The impact of biogeochemical weathering caused by exudates of plants, fungi and bacteria containing siderophores has been discussed. We have studied the dissolution kinetics of Mn-substituted goethites (mol % Mn < 11) in the presences of 80 μM desferrioxamine B (DFO-B), a common and well-studied hydroxamate siderophore that has been identified in both terrestrial and marine environments and which forms very stable 1:1 complexes with Fe(III) or Mn(III). (The stability constants at I = 0.1 are 1030.6 and 1028.3, respectively.) A series of Mn-substituted goethites (α-MnxFe1-xOOH) were synthesized from ferrihydrite in the presence of Mn(II) in alkaline media. The Fe(III) in octahedral positions in the mineral structure was partially replaced by Mn, which was confirmed visually by the change to darker color when the content of Mn increased and proved by infra-red spectroscopy and X-ray diffraction studies of the samples. Substitution of Fe in the goethite by Mn caused a change in the cell dimensions. The calculated unit cell edge lengths a and c decreased, while b increased, for the Mn-goethites compared to pure goethite. The difference of the unit cell parameters between the pure goethite and the Mn-substituted goethites increased with increased Mn content, providing further confirmation that Fe had been substituted by Mn incorporated into the goethite structure. X-ray absorption near-edge structure spectroscopy analysis of the Mn-substituted goethites showed that the oxidation state of Mn in the samples was, as expected, Mn(III), even when Mn-goethites were prepared from Mn(II) solutions. Both SEM and TEM micrographs showed that the Mn-substituted goethite crystals had the same acicular shape as pure goethite. The specific surface area

  19. NH3-promoted ligand lability in eleven-vertex rhodathiaboranes.

    PubMed

    Calvo, Beatriz; Roy, Beatriz; Macías, Ramón; Artigas, Maria Jose; Lahoz, Fernando J; Oro, Luis A

    2014-12-01

    The reaction of the 11-vertex rhodathiaborane, [8,8-(PPh3)2-nido-8,7-RhSB9H10] (1), with NH3 affords inmediately the adduct, [8,8,8-(NH3)(PPh3)2-nido-8,7-RhSB9H10] (4). The NH3-Rh interaction induces the labilization of the PPh3 ligands leading to the dissociation product, [8,8-(NH3)(PPh3)-nido-8,7-RhSB9H10] (5), which can then react with another molecule of NH3 to give [8,8,8-(NH3)2(PPh3)-nido-8,7-RhSB9H10] (6). These clusters have been characterized in situ by multielement NMR spectroscopy at different temeperatures. The variable temperature behavior of the system demonstrates that the intermediates 4-6 are in equilibrium, involving ligand exchange processes. On the basis of low intensity signals present in the (1)H NMR spectra of the reaction mixture, some species are tentatively proposed to be the bis- and tris-NH3 ligated clusters, [8,8-(NH3)2-nido-8,7-RhSB9H10] (7) and [8,8,8-(NH3)3-nido-8,7-RhSB9H10] (8). After evaporation of the solvent and the excess of NH3, the system containing species 4-8 regenerates the starting reactant, 1, thus closing a stoichiometric cycle of ammonia addition and loss. After 40 h at room temperature, the reaction of 1 with NH3 gives the hydridorhodathiaborane, [8,8,8-(H)(PPh3)2-nido-8,7-RhSB9H9] (2), as a single product. The reported rhodathiaboranes show reversible H3N-promoted ligand lability, which implies weak Rh-N interactions, leading to a rare case of metal complexes that circumvent "classical" Werner chemistry.

  20. Intracrystalline Proteins Promote Dissolution of Urinary Calcium Oxalate Crystals in Cultured Renal Epithelial Cells

    NASA Astrophysics Data System (ADS)

    Grover, Phulwinder K.; Thurgood, Lauren A.; Fleming, David E.; van Bronswijk, Wilhelm; Ryall, Rosemary L.

    2007-04-01

    We have proposed that internalized calcium oxalate (CaOx) crystals containing intracrystalline proteins would be vulnerable to intracellular dissolution. The aims of this study were (1) to measure non-uniform strain and crystallite size in CaOx monohydrate (COM) crystals containing increasing amounts of intracrystalline crystal matrix extract (CME) and (2) to compare the rates of crystal dissolution in Madin-Darby canine kidney (MDCKII) cells. CME was isolated by demineralization of COM crystals generated from human urine. Cold and 14C-oxalate-labelled COM crystals were precipitated from ultrafiltered urine containing CME at final concentrations of 0-5mg/L. Non-uniform strain and crystallite size were determined using synchrotron X-ray diffraction with Rietveld whole-pattern peak fitting and profile analysis, and the protein content of the crystals was analyzed using SDS-PAGE and Western blotting for prothrombin fragment 1. Radiolabeled crystals were added to MDCKII cells and dissolution was expressed as radioactive label released into the medium relative to that in the crystals at zero time. Non-uniform strain increased and crystallite size decreased proportionally with rising CME concentration, reaching saturation between approximately 1 and 5 mg/L, and demonstrating unequivocally the inclusion of increasing quantities of proteins in the crystals. This was confirmed by SDS-PAGE and Western blotting. Crystal dissolution also followed saturation kinetics. These findings were confirmed by field emission scanning electron microscopy (FESEM), which showed that the degree of crystal degradation increased relative to CME concentration. We conclude that intracrystalline proteins enhance intracellular dissolution of CaOx crystals and thus may provide a natural defense against stone pathogenesis.

  1. Catalytic asymmetric bromochlorination of aromatic allylic alcohols promoted by multifunctional Schiff base ligands.

    PubMed

    Huang, Wei-Sheng; Chen, Li; Zheng, Zhan-Jiang; Yang, Ke-Fang; Xu, Zheng; Cui, Yu-Ming; Xu, Li-Wen

    2016-08-16

    It was found that the tridentate O,N,O-type Schiff base ligand bearing suitable substituents was a highly effective promoter in the catalytic asymmetric bromochlorination reaction, in which the corresponding aromatic bromochloroalcohols with vicinal halogen-bearing stereocenters were formed with perfect regioselectivity, with moderate to excellent enantioselectivities (up to 93% ee), and with good yields and chemoselectivities. PMID:27488387

  2. Solvent exchange in AlF{sub x} (H{sub 2}O){sup 3-x}{sub 6-x} (aq) complexes: Ligand-directed labilization of water as an analogue for ligand-induced dissolution of oxide minerals

    SciTech Connect

    Phillips, B.L.; Casey, W.H.; Crawford, S.N.

    1997-08-01

    We demonstrate, using dynamic {sup 17}O-NMR spectroscopy, that fluoride ions in the inner-coordination sphere of AlF{sub x} (H{sub 2}O){sub 6-x}{sup 3-x} (aq) complexes (0 {le} x {le} 2) progressively enhance, by orders of magnitude, the rate of exchange of waters from the innersphere to the bulk solvent. At 298K, the rate of the elementary ligand-exchange reaction increased approximately linearly with each fluoride substitution from about 2 s{sup -1} for the fully hydrated [Al(H{sub 2}O){sub 4}{sup +} (aq).] complex. A similar effect can be expected for isoelectronic complexes, such as the hydrolysis product: AlOH (H{sub 2}O){sub 5}{sup 2+} (aq). By hypothesis, a similar phenomenon accounts for fluoride-enhanced release of metals from a dissolving mineral surface. If so, it should be possible to predict the effectiveness of different adsorbed ligands to enhance dissolution of minerals from spectroscopic rate measurements on dissolved complexes, as was recently shown for aminocarboxylate ligands and NiO(s). 42 refs., 6 figs., 3 tabs.

  3. Mechanisms for fluoride-promoted dissolution of bayerite [{beta}-Al(OH){sub 3}(s)] and boehmite [{gamma}-AlOOH]: {sup 19}F-NMR spectroscopy and aqueous surface chemistry

    SciTech Connect

    Nordin, J.P.; Sullivan, D.J.; Phillips, B.L.; Casey, W.H.

    1999-11-01

    Some reactions that control the dissolution of bayerite [{beta}-Al(OH){sub 3}(s)] and boehmite [{gamma}-AlOOH] were identified by comparing the adsorption chemistry, the dissolution rates, and solid-state {sup 19}F-NMR spectra of the reacting surfaces. The {sup 19}F-NMR spectra of bayerite distinguish two sites for fluoride reaction that vary in relative concentration with the total adsorbate density. One resonance at {minus}131 ppm is assigned to fluoride bridges and the other resonance at {minus}142 ppm is assigned to fluoride at terminal sites. These same resonances are observed on boehmite, in addition to a third resonance at {minus}151 ppm that is tentatively assigned to aqueous AlF{sub n}(H{sub 2}O){sub 6{minus}n}{sup (3{minus}n)+} (aq) complexes in pores. Peak broadening due to dipolar coupling between surface fluorides at high loading indicates that these sites are in close proximity. A consistent picture of dissolution is derived by considering the {sup 19}F-NMR results, the aqueous experiments, and information derived from the studies of aqueous complexes, particularly studies of the dissociation mechanisms of aqueous multimers. Both fluoride and adsorbed proton enhance the dissolution rates via a series of pathways that may be coupled to one another, and there is a profound dependence of the rate on the concentration of adsorbed protons and adsorbed fluorides. Particularly important are fluoride-substituted bridges and sites where aluminum atoms are bonded to several terminal fluorides or hydroxyls. These results illustrate that it is possible to test hypotheses about molecular-scale processes if adsorption studies are coupled to spectroscopy and ligand-promoted dissolution experiments where reaction via different pathways can be distinguished.

  4. Ligand-Promoted, Boron-Mediated Chemoselective Carboxylic Acid Aldol Reaction.

    PubMed

    Nagai, Hideoki; Morita, Yuya; Shimizu, Yohei; Kanai, Motomu

    2016-05-01

    The first carboxylic acid selective aldol reaction mediated by boron compounds and a mild organic base (DBU) was developed. Inclusion of electron-withdrawing groups in the amino acid derivative ligands reacted with BH3·SMe2 forms a boron promoter with increased Lewis acidity at the boron atom and facilitated the carboxylic acid selective enolate formation, even in the presence of other carbonyl groups such as amides, esters, ketones, or aliphatic aldehydes. The remarkable ligand effect led to the broad substrate scope including biologically relevant compounds. PMID:27104352

  5. Ligand-Promoted Meta-C-H Arylation of Anilines, Phenols, and Heterocycles.

    PubMed

    Wang, Peng; Farmer, Marcus E; Huo, Xing; Jain, Pankaj; Shen, Peng-Xiang; Ishoey, Mette; Bradner, James E; Wisniewski, Steven R; Eastgate, Martin D; Yu, Jin-Quan

    2016-07-27

    Here we report the development of a versatile 3-acetylamino-2-hydroxypyridine class of ligands that promote meta-C-H arylation of anilines, heterocyclic aromatic amines, phenols, and 2-benzyl heterocycles using norbornene as a transient mediator. More than 120 examples are presented, demonstrating this ligand scaffold enables a wide substrate and coupling partner scope. Meta-C-H arylation with heterocyclic aryl iodides as coupling partners is also realized for the first time using this ligand. The utility for this transformation for drug discovery is showcased by allowing the meta-C-H arylation of a lenalidomide derivative. The first steps toward a silver-free protocol for this reaction are also demonstrated. PMID:27384126

  6. The CXCL12/CXCR4 axis promotes ligand-independent activation of the androgen receptor.

    PubMed

    Kasina, Sathish; Macoska, Jill A

    2012-04-01

    The molecular mechanisms responsible for the transition of some prostate cancers from androgen ligand-dependent to androgen ligand-independent are incompletely established. Molecules that are ligands for G protein coupled receptors (GPCRs) have been implicated in ligand-independent androgen receptor (AR) activation. The purpose of this study was to examine whether CXCL12, the ligand for the GPCR, CXCR4, might mediate prostate cancer cell proliferation through AR-dependent mechanisms involving functional transactivation of the AR in the absence of androgen. The results of these studies showed that activation of the CXCL12/CXCR4 axis promoted: The nuclear accumulation of both wild-type and mutant AR in several prostate epithelial cell lines; AR-dependent proliferative responses; nuclear accumulation of the AR co-regulator SRC-1 protein; SRC-1:AR protein:protein association; co-localization of AR and SRC-1 on the promoters of AR-regulated genes; AR- and SRC-1 dependent transcription of AR-regulated genes; AR-dependent secretion of the AR-regulated PSA protein; P13K-dependent phosphorylation of AR; MAPK-dependent phosphorylation of SRC-1, and both MAPK- and P13K-dependent secretion of the PSA protein, in the absence of androgen. Taken together, these studies identify CXCL12 as a novel, non-steroidal growth factor that promotes the growth of prostate epithelial cells through AR-dependent mechanisms in the absence of steroid hormones. These findings support the development of novel therapeutics targeting the CXCL12/CXCR4 axis as an ancillary to those targeting the androgen/AR axis to effectively treat castration resistant/recurrent prostate tumors.

  7. Ligand-Promoted Borylation of C(sp(3))-H Bonds with Palladium(II) Catalysts.

    PubMed

    He, Jian; Jiang, Heng; Takise, Ryosuke; Zhu, Ru-Yi; Chen, Gang; Dai, Hui-Xiong; Dhar, T G Murali; Shi, Jun; Zhang, Hao; Cheng, Peter T W; Yu, Jin-Quan

    2016-01-11

    A quinoline-based ligand effectively promotes the palladium-catalyzed borylation of C(sp(3))-H bonds. Primary β-C(sp(3))-H bonds in carboxylic acid derivatives as well as secondary C(sp(3))-H bonds in a variety of carbocyclic rings, including cyclopropanes, cyclobutanes, cyclopentanes, cyclohexanes, and cycloheptanes, can thus be borylated. This directed borylation method complements existing iridium(I)- and rhodium(I)-catalyzed C-H borylation reactions in terms of scope and operational conditions.

  8. Toll-like receptor 2 ligands promote microglial cell death by inducing autophagy

    PubMed Central

    Arroyo, Daniela S.; Soria, Javier A.; Gaviglio, Emilia A.; Garcia-Keller, Constanza; Cancela, Liliana M.; Rodriguez-Galan, Maria C.; Wang, Ji Ming; Iribarren, Pablo

    2013-01-01

    Microglial cells are phagocytes in the central nervous system (CNS) and become activated in pathological conditions, resulting in microgliosis, manifested by increased cell numbers and inflammation in the affected regions. Thus, controlling microgliosis is important to prevent pathological damage to the brain. Here, we evaluated the contribution of Toll-like receptor 2 (TLR2) to microglial survival. We observed that activation of microglial cells with peptidoglycan (PGN) from Staphylococcus aureus and other TLR2 ligands results in cell activation followed by the induction of autophagy and autophagy-dependent cell death. In C57BL/6J mice, intracerebral injection of PGN increased the autophagy of microglial cells and reduced the microglial/macrophage cell number in brain parenchyma. Our results demonstrate a novel role of TLRs in the regulation of microglial cell activation and survival, which are important for the control of microgliosis and associated inflammatory responses in the CNS.—Arroyo, D. S., Soria, J. A., Gaviglio, E. A., Garcia-Keller, C., Cancela, L. M., Rodriguez-Galan, M. C., Wang, J. M., Iribarren, P. Toll-like receptor 2 ligands promote microglial cell death by inducing autophagy. PMID:23073832

  9. WISP-3 functions as a ligand and promotes superoxide dismutase activity.

    PubMed

    Davis, Leila; Chen, Yi; Sen, Malini

    2006-03-31

    WISP-3 (Wnt1 inducible secreted protein-3) mutations have been linked to the connective tissue diseases progressive pseudorheumatoid dysplasia and polyarticular juvenile idiopathic arthritis, both of which are accompanied by disorders in cartilage maintenance/homeostasis. The molecular mechanism of WISP-3 mediated effects in the sustenance of cartilage has not been described in detail. Our previous study illustrates the potential role of WISP-3 in regulating the expression of cartilage-specific molecules that sustain chondrocyte growth and cartilage integrity. The present study was conducted to investigate the mode of action of WISP-3 in greater detail. Experimental results depicted here suggest that WISP-3 can function as a ligand and signal via autocrine and/or paracrine modes upon being secreted by chondrocytes. Furthermore, apart from regulating collagen II and aggrecan expression, WISP-3 may also promote superoxide dismutase expression and activity in chondrocytes.

  10. The effect of microbial glucose metabolism on bytownite feldspar dissolution rates between 5 and 35 C

    SciTech Connect

    Welch, S.A.; Ullman, W.J.

    1999-10-01

    The rate of Si release from dissolving bytownite feldspar in abiotic batch reactors increased as temperatures increased from 5 to 35 C. Metabolically inert subsurface bacteria (bacteria in solution with no organic substrate) had no apparent effect on dissolution rates over this temperature range. When glucose was added to the microbial cultures, the bacteria responded by producing gluconic acid, which catalyzed the dissolution reaction by both proton- and ligand-promoted mechanisms. The metabolic production, excretion, and consumption of gluconic acid in the course of glucose oxidation, and therefore, the degree of microbial enhancement of mineral dissolution, depend on temperature. There was little accumulation of gluconic acid and therefore, no significant enhancement of mineral dissolution rates at 35 C compared to the abiotic controls. At 20 C, gluconate accumulated in the experimental solutions only at the beginning of the experiment and led to a twofold increase in dissolved Si release compared to the controls, primarily by the ligand-promoted dissolution mechanism. There was significant accumulation of gluconic acid in the 5 C experiment, which is reflected in a significant reduction in pH, leading to 20-fold increase in Si release, primarily attributable to the proton-promoted dissolution mechanism. These results indicate that bacteria and microbial metabolism can affect mineral dissolution rates in organic-rich, nutrient-poor environments; the impact of microbial metabolism on aluminum silicate dissolution rates may be greater at lower rather than at higher temperatures due to the metabolic accumulation of dissolution-enhancing protons and ligands in solution.

  11. The coordination chemistry of weathering: I. Dissolution kinetics of δ- Al2O3 and BeO

    NASA Astrophysics Data System (ADS)

    Furrer, Gerhard; Stumm, Werner

    1986-09-01

    The dissolution kinetics of most slightly soluble oxides and silicates are controlled by chemical processes at the surface. The reaction controlling steps can be interpreted in terms of a surface coordination model. In dilute acid solutions, in the absence of complex-forming ligands, the dissolution kinetics are controlled by the surface bound protons. The rate of the proton-promoted reaction of δ- Al2O3 is RH = kH( CH3) 3 where C h3 is the proton concentration per unit area on the oxide surface. The mechanism can be described by the attachment of three protons to the reaction site prior to the detachment of an Al species into the solution. The dissolution rate of BeO is proportional to (C H2) 2. For δ- Al2O3 at pH ⩽ 3.5 dissolution rate is independent of pH; at this pH maximum surface concentration of protons is reached. The organic ligand-promoted dissolution, RL, is of first order with respect to concentration of surface chelates: R L = k L{M ?L} where {M ?L} is the concentration of surface chelates per unit area. Detachable surface complexes result from surface coordination of metal ions of the hydrous oxides with bidentate ligands. Especially efficient are bidentate ligands that form mononuclear surface complexes. The sequence of rate constants shows that five- and six-membered chelate rings (oxalate, catechol, malonate and salicylate) enhance the dissolution reactions to a greater extent than seven-membered rings (phthalate, succinate). Monodentate ligands (benzoate ion), though readily adsorbed, do not enhance dissolution rates. However, they can inhibit dissolution by displacing ligands that catalyze this reaction.

  12. Self-assembly of colloidal nanocrystals: Surface ligands promote the formation of unexpected superlattices

    NASA Astrophysics Data System (ADS)

    Boles, Michael Adam

    The advent and refinement of chemical techniques to produce uniform collections of colloidal nanocrystals in recent years has made accessible a wide range of nanocrystal materials, shapes, and sizes, offering a fertile testbed for developing an understanding of nanoscale crystallization. Elucidating the role of nanocrystal surfaces in promoting self-assembly of superlattice phases unanticipated by hard-shape packing models has been the focus of my graduate work. Chapter One provides a practical overview of the experimental approaches to prepare and characterize colloidal nanocrystals and self-assembled nanocrystal superlattices. Chapter Two discusses colloidal nanocrystal surfaces including atomic composition, chemical reactivity, and influence over electronic structure. Chapter Three provides an overview of nanocrystal self-assembly including interparticle potentials and predicted phase behavior for hard and soft shapes. Chapter Four describes the preparation of tetrahedrally-shaped CdSe nanocrystals and their self-assembly into an unexpected superlattice structure. Chapter Five presents a selection of electron microscopy images of superlattices comprised of nearly spherical nanocrystals. Chapter Six describes the application of image analysis techniques to elucidate ligand shell deformability of spherical nanocrystals and resulting implications for entropy-driven crystallization of soft objects. Chapter Seven analyzes the role of PbS surface ligand desorption in determining binary phase behavior with Au nanocrystals. Chapter Eight describes the implications of the ideas presented in this thesis, places them in the context of recent work by others in the field, and offers an outlook towards promising directions for future research. Together, the ideas contained herein aim to provide the conceptual foundation necessary to exploit nanocrystal self-assembly for the rational design of next-generation functional solids.

  13. OX40 Ligand Contributes to Human Lupus Pathogenesis by Promoting T Follicular Helper Response.

    PubMed

    Jacquemin, Clément; Schmitt, Nathalie; Contin-Bordes, Cécile; Liu, Yang; Narayanan, Priya; Seneschal, Julien; Maurouard, Typhanie; Dougall, David; Davizon, Emily Spence; Dumortier, Hélène; Douchet, Isabelle; Raffray, Loïc; Richez, Christophe; Lazaro, Estibaliz; Duffau, Pierre; Truchetet, Marie-Elise; Khoryati, Liliane; Mercié, Patrick; Couzi, Lionel; Merville, Pierre; Schaeverbeke, Thierry; Viallard, Jean-François; Pellegrin, Jean-Luc; Moreau, Jean-François; Muller, Sylviane; Zurawski, Sandy; Coffman, Robert L; Pascual, Virginia; Ueno, Hideki; Blanco, Patrick

    2015-06-16

    Increased activity of T follicular helper (Tfh) cells plays a major pathogenic role in systemic lupus erythematosus (SLE). However, the mechanisms that cause aberrant Tfh cell responses in SLE remain elusive. Here we showed the OX40 ligand (OX40L)-OX40 axis contributes to the aberrant Tfh response in SLE. OX40L was expressed by myeloid antigen-presenting cells (APCs), but not B cells, in blood and in inflamed tissues in adult and pediatric SLE patients. The frequency of circulating OX40L-expressing myeloid APCs positively correlated with disease activity and the frequency of ICOS(+) blood Tfh cells in SLE. OX40 signals promoted naive and memory CD4(+) T cells to express multiple Tfh cell molecules and were sufficient to induce them to become functional B cell helpers. Immune complexes containing RNA induced OX40L expression on myeloid APCs via TLR7 activation. Our study provides a rationale to target the OX40L-OX40 axis as a therapeutic modality for SLE. PMID:26070486

  14. An L-selectin ligand distinct from P-selectin glycoprotein ligand-1 is expressed on endothelial cells and promotes neutrophil rolling in inflammation.

    PubMed

    Shigeta, Akiko; Matsumoto, Masanori; Tedder, Thomas F; Lowe, John B; Miyasaka, Masayuki; Hirata, Takako

    2008-12-15

    Neutrophils recruited from the blood are key players in the innate immune response. Selectins play critical roles in neutrophil recruitment by mediating their tethering and rolling in inflamed venules. While the roles of P- and E-selectin in this process are well established, the mechanisms of L-selectin-mediated neutrophil recruitment remain elusive. One proposal is that tethering is mediated by L-selectin on flowing neutrophils interacting with P-selectin glycoprotein ligand-1 (PSGL-1) on adherent neutrophils. To clarify whether L-selectin-mediated neutrophil recruitment depends entirely on PSGL-1, we examined the impact of L-selectin deficiency in mice with a PSGL-1-deficient background. L-selectin and PSGL-1 double-knockout mice exhibited a higher increase in their peripheral blood neutrophil count and a worse defect in neutrophil recruitment into the inflamed peritoneum than PSGL-1-deficient mice. Intravital microscopy of inflamed cremaster muscle venules showed that L-selectindeficiency or antibody blockade of L-selectin reduced the residual leukocyte rolling in PSGL-1-deficient mice. Flow cytometric analyses showed that the endothelial cells from the cremaster muscle bound L-selectin in a PSGL-1-independent manner. These results provide evidence for the existence of an L-selectin ligand distinct from PSGL-1 in inflammation and indicate that such a ligand is expressed on endothelial cells, promoting neutrophil rolling in vivo.

  15. An L-selectin ligand distinct from P-selectin glycoprotein ligand-1 is expressed on endothelial cells and promotes neutrophil rolling in inflammation

    PubMed Central

    Shigeta, Akiko; Matsumoto, Masanori; Tedder, Thomas F.; Lowe, John B.; Miyasaka, Masayuki

    2008-01-01

    Neutrophils recruited from the blood are key players in the innate immune response. Selectins play critical roles in neutrophil recruitment by mediating their tethering and rolling in inflamed venules. While the roles of P- and E-selectin in this process are well established, the mechanisms of L-selectin–mediated neutrophil recruitment remain elusive. One proposal is that tethering is mediated by L-selectin on flowing neutrophils interacting with P-selectin glycoprotein ligand-1 (PSGL-1) on adherent neutrophils. To clarify whether L-selectin–mediated neutrophil recruitment depends entirely on PSGL-1, we examined the impact of L-selectin deficiency in mice with a PSGL-1–deficient background. L-selectin and PSGL-1 double-knockout mice exhibited a higher increase in their peripheral blood neutrophil count and a worse defect in neutrophil recruitment into the inflamed peritoneum than PSGL-1–deficient mice. Intravital microscopy of inflamed cremaster muscle venules showed that L-selectindeficiency or antibody blockade of L-selectin reduced the residual leukocyte rolling in PSGL-1–deficient mice. Flow cytometric analyses showed that the endothelial cells from the cremaster muscle bound L-selectin in a PSGL-1–independent manner. These results provide evidence for the existence of an L-selectin ligand distinct from PSGL-1 in inflammation and indicate that such a ligand is expressed on endothelial cells, promoting neutrophil rolling in vivo. PMID:18818390

  16. The effect of microbial glucose metabolism on bytownite feldspar dissolution rates between 5° and 35°C

    NASA Astrophysics Data System (ADS)

    Welch, S. A.; Ullman, W. J.

    1999-10-01

    The rate of Si release from dissolving bytownite feldspar in abiotic batch reactors increased as temperatures increased from 5° to 35°C. Metabolically inert subsurface bacteria (bacteria in solution with no organic substrate) had no apparent effect on dissolution rates over this temperature range. When glucose was added to the microbial cultures, the bacteria responded by producing gluconic acid, which catalyzed the dissolution reaction by both proton- and ligand-promoted mechanisms. The metabolic production, excretion, and consumption of gluconic acid in the course of glucose oxidation, and therefore, the degree of microbial enhancement of mineral dissolution, depend on temperature. There was little accumulation of gluconic acid and therefore, no significant enhancement of mineral dissolution rates at 35°C compared to the abiotic controls. At 20°C, gluconate accumulated in the experimental solutions only at the beginning of the experiment and led to a twofold increase in dissolved Si release compared to the controls, primarily by the ligand-promoted dissolution mechanism. There was significant accumulation of gluconic acid in the 5°C experiment, which is reflected in a significant reduction in pH, leading to 20-fold increase in Si release, primarily attributable to the proton-promoted dissolution mechanism. These results indicate that bacteria and microbial metabolism can affect mineral dissolution rates in organic-rich, nutrient-poor environments; the impact of microbial metabolism on aluminum silicate dissolution rates may be greater at lower rather than at higher temperatures due to the metabolic accumulation of dissolution-enhancing protons and ligands in solution.

  17. Atmospheric Dissolved Iron Depostiion to the Global Oceans: Effects of Oxalate-Promoted Fe Dissolution, Photochemical Redox Cycling, and Dust Mineralogy

    NASA Technical Reports Server (NTRS)

    Johnson, M. S.; Meskhidze, N.

    2013-01-01

    Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fed) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fed production during the atmospheric transport of mineral dust taking into account inorganic and organic (oxalate)-promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of windblown dust from the major desert regions. Our calculations suggest that during the yearlong simulation is approximately 0.26 Tg (1 Tg = 1012 g) of Fed was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate to the dust-Fe mobilization scheme increased total annual model-predicted Fed deposition to global oceanic regions by approximately 75%. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model allows for the distinction between different oxidation states of deposited Fed. Our calculations suggest that during the daytime, large fractions of Fed deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fed are largely in Fe(III) form. Model simulations also show that atmospheric fluxes of Fed can be strongly influenced by the mineralogy of Fe-containing compounds. This study shows that Fed deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the

  18. A shed NKG2D ligand that promotes natural killer cell activation and tumor rejection

    PubMed Central

    Deng, Weiwen; Gowen, Benjamin G.; Zhang, Li; Wang, Lin; Lau, Stephanie; Iannello, Alexandre; Xu, Jianfeng; Rovis, Tihana L.; Xiong, Na; Raulet, David H.

    2016-01-01

    Immune cells, including natural killer (NK) cells, recognize transformed cells and eliminate them in a process termed immunosurveillance. It is thought that tumor cells evade immunosurveillance by shedding membrane ligands that bind to the NKG2D activating receptor on NK cells and/or T cells, and desensitize these cells. In contrast, we show that in mice, shedding of MULT1, a high affinity NKG2D ligand, causes NK cell activation and tumor rejection. Recombinant soluble MULT1 stimulated tumor rejection in mice. Soluble MULT1 functions, at least in part, by competitively reversing a global desensitization of NK cells imposed by engagement of membrane NKG2D ligands on tumor-associated cells, such as myeloid cells. The results overturn conventional wisdom that soluble ligands are inhibitory, and suggest a new approach for cancer immunotherapy. PMID:25745066

  19. TSPO PIGA Ligands Promote Neurosteroidogenesis and Human Astrocyte Well-Being

    PubMed Central

    Da Pozzo, Eleonora; Giacomelli, Chiara; Costa, Barbara; Cavallini, Chiara; Taliani, Sabrina; Barresi, Elisabetta; Da Settimo, Federico; Martini, Claudia

    2016-01-01

    The steroidogenic 18 kDa translocator protein (TSPO) is an emerging, attractive therapeutic tool for several pathological conditions of the nervous system. Here, 13 high affinity TSPO ligands belonging to our previously described N,N-dialkyl-2-phenylindol-3-ylglyoxylamide (PIGA) class were evaluated for their potential ability to affect the cellular Oxidative Metabolism Activity/Proliferation index, which is used as a measure of astrocyte well-being. The most active PIGA ligands were also assessed for steroidogenic activity in terms of pregnenolone production, and the values were related to the metabolic index in rat and human models. The results showed a positive correlation between the increase in the Oxidative Metabolism Activity/Proliferation index and the pharmacologically induced stimulation of steroidogenesis. The specific involvement of steroid molecules in mediating the metabolic effects of the PIGA ligands was demonstrated using aminoglutethimide, a specific inhibitor of the first step of steroid biosynthesis. The most promising steroidogenic PIGA ligands were the 2-naphthyl derivatives that showed a long residence time to the target, in agreement with our previous data. In conclusion, TSPO ligand-induced neurosteroidogenesis was involved in astrocyte well-being. PMID:27367681

  20. TSPO PIGA Ligands Promote Neurosteroidogenesis and Human Astrocyte Well-Being.

    PubMed

    Da Pozzo, Eleonora; Giacomelli, Chiara; Costa, Barbara; Cavallini, Chiara; Taliani, Sabrina; Barresi, Elisabetta; Da Settimo, Federico; Martini, Claudia

    2016-06-29

    The steroidogenic 18 kDa translocator protein (TSPO) is an emerging, attractive therapeutic tool for several pathological conditions of the nervous system. Here, 13 high affinity TSPO ligands belonging to our previously described N,N-dialkyl-2-phenylindol-3-ylglyoxylamide (PIGA) class were evaluated for their potential ability to affect the cellular Oxidative Metabolism Activity/Proliferation index, which is used as a measure of astrocyte well-being. The most active PIGA ligands were also assessed for steroidogenic activity in terms of pregnenolone production, and the values were related to the metabolic index in rat and human models. The results showed a positive correlation between the increase in the Oxidative Metabolism Activity/Proliferation index and the pharmacologically induced stimulation of steroidogenesis. The specific involvement of steroid molecules in mediating the metabolic effects of the PIGA ligands was demonstrated using aminoglutethimide, a specific inhibitor of the first step of steroid biosynthesis. The most promising steroidogenic PIGA ligands were the 2-naphthyl derivatives that showed a long residence time to the target, in agreement with our previous data. In conclusion, TSPO ligand-induced neurosteroidogenesis was involved in astrocyte well-being.

  1. TNF-related apoptosis-inducing ligand promotes human preadipocyte proliferation via ERK1/2 activation

    PubMed Central

    Funcke, Jan-Bernd; Zoller, Verena; El Hay, Muad Abd; Debatin, Klaus-Michael; Wabitsch, Martin; Fischer-Posovszky, Pamela

    2015-01-01

    Upon obesity, adipose tissue is excessively expanded and characterized by pathologic processes like hypoxia, fibrosis, and inflammation. Death ligands belonging to the TNF superfamily such as TNF-α are important contributors to these derangements and exert a pronounced influence on the metabolic and cellular homeostasis of adipose tissue. Here, we sought to identify the effect of the death ligand TNF-related apoptosis-inducing ligand (TRAIL) on the adipose tissue precursor cell pool and therefore investigated its influence on preadipocyte proliferation. Treatment of human preadipocytes with TRAIL resulted in a time- and dose-dependent increase in proliferation (EC50 3.4 ng/ml) comparable to IGF-1. Although no apoptosis was observed, TRAIL triggered a rapid cleavage of caspase-8 and -3. Neither inhibition of caspase activity by zVAD.fmk (20 µM) nor ablation of caspase-8 expression by lentivirus-delivered small hairpin RNA (shRNA) abolished the proliferative response. TRAIL triggered a delayed and sustained activation of ERK1/2, leaving Akt, p38, JNK, and NF-κB unaffected. Importantly, inhibition of ERK1/2 activation by PD0325901 (300 nM) or AZD6244 (5 or 10 µM) completely abolished the proliferative response. We thus reveal a hitherto unknown function of TRAIL in regulating adipose tissue homeostasis by promoting the proliferation of tissue-resident precursor cells.—Funcke, J.-B., Zoller, V., Abd El Hay, M., Debatin, K.-M., Wabitsch, M., Fischer-Posovszky, P. TNF-related apoptosis-inducing ligand promotes human preadipocyte proliferation via ERK1/2 activation. PMID:25857555

  2. TNF-related apoptosis-inducing ligand promotes human preadipocyte proliferation via ERK1/2 activation.

    PubMed

    Funcke, Jan-Bernd; Zoller, Verena; El Hay, Muad Abd; Debatin, Klaus-Michael; Wabitsch, Martin; Fischer-Posovszky, Pamela

    2015-07-01

    Upon obesity, adipose tissue is excessively expanded and characterized by pathologic processes like hypoxia, fibrosis, and inflammation. Death ligands belonging to the TNF superfamily such as TNF-α are important contributors to these derangements and exert a pronounced influence on the metabolic and cellular homeostasis of adipose tissue. Here, we sought to identify the effect of the death ligand TNF-related apoptosis-inducing ligand (TRAIL) on the adipose tissue precursor cell pool and therefore investigated its influence on preadipocyte proliferation. Treatment of human preadipocytes with TRAIL resulted in a time- and dose-dependent increase in proliferation (EC50 3.4 ng/ml) comparable to IGF-1. Although no apoptosis was observed, TRAIL triggered a rapid cleavage of caspase-8 and -3. Neither inhibition of caspase activity by zVAD.fmk (20 µM) nor ablation of caspase-8 expression by lentivirus-delivered small hairpin RNA (shRNA) abolished the proliferative response. TRAIL triggered a delayed and sustained activation of ERK1/2, leaving Akt, p38, JNK, and NF-κB unaffected. Importantly, inhibition of ERK1/2 activation by PD0325901 (300 nM) or AZD6244 (5 or 10 µM) completely abolished the proliferative response. We thus reveal a hitherto unknown function of TRAIL in regulating adipose tissue homeostasis by promoting the proliferation of tissue-resident precursor cells. PMID:25857555

  3. TNF-related apoptosis-inducing ligand promotes human preadipocyte proliferation via ERK1/2 activation.

    PubMed

    Funcke, Jan-Bernd; Zoller, Verena; El Hay, Muad Abd; Debatin, Klaus-Michael; Wabitsch, Martin; Fischer-Posovszky, Pamela

    2015-07-01

    Upon obesity, adipose tissue is excessively expanded and characterized by pathologic processes like hypoxia, fibrosis, and inflammation. Death ligands belonging to the TNF superfamily such as TNF-α are important contributors to these derangements and exert a pronounced influence on the metabolic and cellular homeostasis of adipose tissue. Here, we sought to identify the effect of the death ligand TNF-related apoptosis-inducing ligand (TRAIL) on the adipose tissue precursor cell pool and therefore investigated its influence on preadipocyte proliferation. Treatment of human preadipocytes with TRAIL resulted in a time- and dose-dependent increase in proliferation (EC50 3.4 ng/ml) comparable to IGF-1. Although no apoptosis was observed, TRAIL triggered a rapid cleavage of caspase-8 and -3. Neither inhibition of caspase activity by zVAD.fmk (20 µM) nor ablation of caspase-8 expression by lentivirus-delivered small hairpin RNA (shRNA) abolished the proliferative response. TRAIL triggered a delayed and sustained activation of ERK1/2, leaving Akt, p38, JNK, and NF-κB unaffected. Importantly, inhibition of ERK1/2 activation by PD0325901 (300 nM) or AZD6244 (5 or 10 µM) completely abolished the proliferative response. We thus reveal a hitherto unknown function of TRAIL in regulating adipose tissue homeostasis by promoting the proliferation of tissue-resident precursor cells.

  4. Recovery of plutonium from HEPA filters by Ce(IV)-promoted dissolution of PuO/sub 2/ and recycle of the cerium promoter

    SciTech Connect

    Leuze, R. E.; Bond, W. D.; Scheitlin, F. M.

    1980-01-01

    The experimental studies carried out included (1) the electrolytic production of Ce(IV) from Ce(III), (2) the leaching of refractory PuO/sub 2/ from HEPA filter materials with maintenance of Ce(IV) concentrations by anodic oxidation during leaching, and (3) evaluation of methods for contacting the HEPA solids with the leaching solution and for separating the solid residue from the leaching liquor. Anodic oxidation of Ce(III) was accomplished with an electric current efficiency of about 85% at current densities of 0.04 to 0.4 A/dm/sup 2/ at a platinum anode. Refractory PuO/sub 2/ was dissolved by a 4.0 M HNO/sub 3/ - 0.1 M Ce(IV) solution in 1.5 h at 100/sup 0/C using stirred-contact leaching of the solids or by recirculating the leachant through a packed column of the solids. Cerium (IV) concentrations were maintained continuously by anodic oxidation throughout leaching. Dissolution times up to 10 h were required unless the HEPA media were oxidized initially in air at 300/sup 0/C to destroy carbonaceous species which consumed Ce(IV) more rapidly than it could be regenerated by anodic oxidation. Leaching solids in packed columns avoided the relatively difficult liquid-solids separation by centrifugation which was required after stirred-contact leaching; however, the solids handling difficulties associated with charging and discharging of the packed columns in a remote environment remain a significant design obstacle. A chemical flowsheet is proposed for the recovery of actinides from HEPA filters. A 4 M HNO/sub 3/ - 0.1 M Ce(IV) nitrate solution is used as the leachant and the Ce(III) is recycled to the leaching operation using bidentate solvent extraction.

  5. The Effect of Microbial Glucose Metabolism on Bytownite Feldspar Dissolution Rates Between 5{sup o} and 35{sup o}C

    SciTech Connect

    Welch, S. A.; Ullman, W. J.

    1999-04-29

    The rate of Si release from dissolving bytownite feldspar in abiotic batch reactors increased as temperatures increased from 5 to 35 C. Metabolically inert subsurface bacteria (bacteria in solution with no organic substrate) had no apparent effect on dissolution rates over this temperature range. When glucose was added to the microbial cultures, the bacteria responded by producing gluconic acid, which catalyzed the dissolution reaction by both proton- and ligand-promoted mechanisms. The metabolic production, excretion, and consumption of gluconic acid in the course of glucose oxidation, and therefore, the degree of microbial enhancement of mineral dissolution, depend on temperature.

  6. Toll-like receptor 2 ligands promote microglial cell death by inducing autophagy.

    PubMed

    Arroyo, Daniela S; Soria, Javier A; Gaviglio, Emilia A; Garcia-Keller, Constanza; Cancela, Liliana M; Rodriguez-Galan, Maria C; Wang, Ji Ming; Iribarren, Pablo

    2013-01-01

    Microglial cells are phagocytes in the central nervous system (CNS) and become activated in pathological conditions, resulting in microgliosis, manifested by increased cell numbers and inflammation in the affected regions. Thus, controlling microgliosis is important to prevent pathological damage to the brain. Here, we evaluated the contribution of Toll-like receptor 2 (TLR2) to microglial survival. We observed that activation of microglial cells with peptidoglycan (PGN) from Staphylococcus aureus and other TLR2 ligands results in cell activation followed by the induction of autophagy and autophagy-dependent cell death. In C57BL/6J mice, intracerebral injection of PGN increased the autophagy of microglial cells and reduced the microglial/macrophage cell number in brain parenchyma. Our results demonstrate a novel role of TLRs in the regulation of microglial cell activation and survival, which are important for the control of microgliosis and associated inflammatory responses in the CNS. PMID:23073832

  7. Kit ligand promotes the transition from primordial to primary follicles after in vitro culture of ovine ovarian tissue.

    PubMed

    Cavalcante, A Y P; Gouveia, B B; Barberino, R S; Lins, T L B G; Santos, L P; Gonçalves, R J S; Celestino, J J H; Matos, M H T

    2016-08-01

    This study evaluated the effects of kit ligand (KL) on the morphology and development of ovine preantral follicles (fresh control) and after 7 days of in vitro culture in α-Minimal Essential Medium (α-MEM; control medium) or the presence of KL (1, 10, 50, 100 or 200 ng/ml). There was an increase in the percentage of primary follicles at the concentration of 100 ng/ml KL, compared with the fresh control, control medium (α-MEM) and the other KL concentrations. Follicle diameter was significantly higher than the control medium only at concentrations of 50 and 100 ng/ml KL. In conclusion, 100 ng/ml KL promoted the transition from primordial to primary follicles (follicular activation) after in vitro culture of ovine ovarian tissue.

  8. Programmed Death Ligand 1 Promotes Early-Life Chlamydia Respiratory Infection-Induced Severe Allergic Airway Disease.

    PubMed

    Starkey, Malcolm R; Nguyen, Duc H; Brown, Alexandra C; Essilfie, Ama-Tawiah; Kim, Richard Y; Yagita, Hideo; Horvat, Jay C; Hansbro, Philip M

    2016-04-01

    Chlamydia infections are frequent causes of respiratory illness, particularly pneumonia in infants, and are linked to permanent reductions in lung function and the induction of asthma. However, the immune responses that protect against early-life infection and the mechanisms that lead to chronic lung disease are incompletely understood. In the current study, we investigated the role of programmed death (PD)-1 and its ligands PD-L1 and PD-L2 in promoting early-life Chlamydia respiratory infection, and infection-induced airway hyperresponsiveness (AHR) and severe allergic airway disease in later life. Infection increased PD-1 and PD-L1, but not PD-L2, mRNA expression in the lung. Flow cytometric analysis of whole lung homogenates identified monocytes, dendritic cells, CD4(+), and CD8(+) T cells as major sources of PD-1 and PD-L1. Inhibition of PD-1 and PD-L1, but not PD-L2, during infection ablated infection-induced AHR in later life. Given that PD-L1 was the most highly up-regulated and its targeting prevented infection-induced AHR, subsequent analyses focused on this ligand. Inhibition of PD-L1 had no effect on Chlamydia load but suppressed infection-induced pulmonary inflammation. Infection decreased the levels of the IL-13 decoy receptor in the lung, which were restored to baseline levels by inhibition of PD-L1. Finally, inhibition of PD-L1 during infection prevented subsequent infection-induced severe allergic airways disease in later life by decreasing IL-13 levels, Gob-5 expression, mucus production, and AHR. Thus, early-life Chlamydia respiratory infection-induced PD-L1 promotes severe inflammation during infection, permanent reductions in lung function, and the development of more severe allergic airway disease in later life.

  9. Elevated autocrine chemokine ligand 18 expression promotes oral cancer cell growth and invasion via Akt activation

    PubMed Central

    Hong, Yun; Wu, Tong; Chen, Xiaobing; Xia, Juan; Cheng, Bin

    2016-01-01

    Chemokine (C-C motif) ligand 18 (CCL18) has been implicated in the pathogenesis and progression of various cancers; however, in oral squamous cell carcinoma (OSCC), the role of CCL18 is unknown. In this study, we found that CCL18 was overexpressed in primary OSCC tissues and was associated with an advanced clinical stage. CCL18 was found in both the cytoplasm and cell membrane of OSCC cells and was predominantly produced by cancer epithelial cells, as opposed to tumor-infiltrating macrophages. In vitro studies indicated that the effects of endogenous CCL18 on OSCC cell growth, migration, and invasion could be blocked by treatment with a neutralizing anti-CCL18 antibody or CCL18 knockdown, while exogenous recombinant CCL18 (rCCL18) rescued those effects. Akt was activated in rCCL18-treated OSCC cells, while LY294002, a pan-PI3K inhibitor, abolished both endogenous and exogenous CCL18-induced OSCC cell invasion. In vivo, LY294002 treatment attenuated rCCL18-induced OSCC cell growth. Our results indicate that CCL18 acts in an autocrine manner via Akt activation to stimulate OSCC cell growth and invasion during OSCC progression. They also provide a potential therapeutic target for the treatment of oral cancer. PMID:26919103

  10. hGH promotes megakaryocyte differentiation and exerts a complementary effect with c-Mpl ligands on thrombopoiesis.

    PubMed

    Xu, Yang; Wang, Song; Shen, Mingqiang; Zhang, Zhou; Chen, Shilei; Chen, Fang; Chen, Mo; Zeng, Dongfeng; Wang, Aiping; Zhao, Jinghong; Cheng, Tianmin; Su, Yongping; Wang, Junping

    2014-04-01

    Human growth hormone (hGH) is known to play a functional role in regulating hematopoiesis, although its direct effect on thrombopoiesis is unclear. In this study, we show for the first time that hGH has a distinct capacity to promote the differentiation of human primary megakaryocytes derived from umbilical cord blood CD34(+) cells. In particular, hGH is potent in facilitating proplatelet formation and platelet production from cultured megakaryocytes. The stage- and time-specific activations of extracellular signal-regulated kinase 1/2 and protein kinase B signaling pathways are involved in the action of hGH. Fusion with hGH enhances the effect of a tandem dimer of thrombopoietin mimetic peptide (dTMP) on thrombopoiesis, manifested by a significant acceleration and increase of platelet production, indicating that hGH may exert a complementary and synergistic effect with c-Mpl ligands on thrombopoiesis. Accordingly, the administration of dTMP-growth hormone fusion protein led to a rapid platelet recovery in mice with severe thrombocytopenia induced by 6.5 Gy total body irradiation, thereby markedly abridging the duration of thrombocytopenia crisis (platelets <150 × 10(9)/L), in comparison with high doses of dTMP. These findings demonstrate the functional role of growth hormone in promoting thrombopoiesis and provide a promising avenue for the treatment of severe thrombocytopenia.

  11. FAS and FAS ligand polymorphisms in the promoter regions and risk of gastric cancer in Southern China.

    PubMed

    Wang, Meilin; Wu, Dongmei; Tan, Ming; Gong, Weida; Xue, Hengchuan; Shen, Hongbin; Zhang, Zhengdong

    2009-08-01

    The FAS and FAS ligand (FASLG) system plays a key role in regulating apoptotic cell death, and corruption of this signaling pathway has been shown to participate in tumorigenesis. Functional promoter polymorphisms of the FAS and FASLG genes can alter transcriptional activities and thus alter risk of cancer. We hypothesized that the FAS -1377G>A, FAS -670A>G, and FASLG -844T>C polymorphisms in the promoter regions are associated with risk of gastric cancer. In a population-based case-control study of 332 gastric cancer cases and 324 controls, we genotyped these three polymorphisms and evaluated their association with risk of gastric cancer. We found that the FAS and FASL genotypes and the FAS haplotypes had no significant associations with risk of gastric cancer. In addition, there was no significant interaction between the FAS and FASL polymorphisms in the development of gastric cancer. The FAS and FASLG polymorphisms may not contribute to risk of gastric cancer in the southern Chinese population.

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

    PubMed

    Chen, Haihan; Grassian, Vicki H

    2013-09-17

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

  13. An ABA-mimicking ligand that reduces water loss and promotes drought resistance in plants

    PubMed Central

    Cao, Minjie; Liu, Xue; Zhang, Yan; Xue, Xiaoqian; Zhou, X Edward; Melcher, Karsten; Gao, Pan; Wang, Fuxing; Zeng, Liang; Zhao, Yang; Zhao, Yang; Deng, Pan; Zhong, Dafang; Zhu, Jian-Kang; Xu, H Eric; Xu, Yong

    2013-01-01

    Abscisic acid (ABA) is the most important hormone for plants to resist drought and other abiotic stresses. ABA binds directly to the PYR/PYL family of ABA receptors, resulting in inhibition of type 2C phosphatases (PP2C) and activation of downstream ABA signaling. It is envisioned that intervention of ABA signaling by small molecules could help plants to overcome abiotic stresses such as drought, cold and soil salinity. However, chemical instability and rapid catabolism by plant enzymes limit the practical application of ABA itself. Here we report the identification of a small molecule ABA mimic (AM1) that acts as a potent activator of multiple members of the family of ABA receptors. In Arabidopsis, AM1 activates a gene network that is highly similar to that induced by ABA. Treatments with AM1 inhibit seed germination, prevent leaf water loss, and promote drought resistance. We solved the crystal structure of AM1 in complex with the PYL2 ABA receptor and the HAB1 PP2C, which revealed that AM1 mediates a gate-latch-lock interacting network, a structural feature that is conserved in the ABA-bound receptor/PP2C complex. Together, these results demonstrate that a single small molecule ABA mimic can activate multiple ABA receptors and protect plants from water loss and drought stress. Moreover, the AM1 complex crystal structure provides a structural basis for designing the next generation of ABA-mimicking small molecules. PMID:23835477

  14. Human thymus medullary epithelial cells promote regulatory T-cell generation by stimulating interleukin-2 production via ICOS ligand.

    PubMed

    Nazzal, D; Gradolatto, A; Truffault, F; Bismuth, J; Berrih-Aknin, S

    2014-09-11

    Natural thymic T regulatory (tTreg) cells maintain tolerance to self-antigen. These cells are generated in the thymus, but how this generation occurs is still controversial. Furthermore, the contribution of thymus epithelial cells to this process is still unclear, especially in humans. Using an exceptional panel of human thymic samples, we demonstrated that medullary thymus epithelial cells (mTECs) promote the generation of tTreg cells and favor their function. These effects were mediated through soluble factors and were mTEC specific since other cell types had no such effect. By evaluating the effects of mTECs on the absolute number of Treg cells and their state of proliferation or cell death, we conclude that mTECs promote the proliferation of newly generated CD25+ cells from CD4+CD25- cells and protect Treg cells from cell death. This observation implicates Bcl-2 and mitochondrial membrane potential changes, indicating that the intrinsic cell death pathway is involved in Treg protection by mTECs. Interestingly, when the mTECs were cultured directly with purified Treg cells, they were able to promote their phenotype but not their expansion, suggesting that CD4+CD25- cells have a role in the expansion process. To explore the mechanisms involved, several neutralizing antibodies were tested. The effects of mTECs on Treg cells were essentially due to interleukin (IL)-2 overproduction by thymus CD4+ T cells. We then searched for a soluble factor produced by mTECs able to increase IL-2 production by CD4+ cells and could identify the inducible T-cell costimulator ligand (ICOSL). Our data strongly suggest a « ménage à trois »: mTEC cells (via ICOSL) induce overproduction of IL-2 by CD25- T cells leading to the expansion of tTreg cells. Altogether, these results demonstrate for the first time a role of mTECs in promoting Treg cell expansion in the human thymus and implicate IL-2 and ICOSL in this process.

  15. Antimony-based ligand exchange to promote crystallization in spray-deposited Cu2ZnSnSe4 solar cells.

    PubMed

    Carrete, Alex; Shavel, Alexey; Fontané, Xavier; Montserrat, Joana; Fan, Jiandong; Ibáñez, Maria; Saucedo, Edgardo; Pérez-Rodríguez, Alejandro; Cabot, Andreu

    2013-10-30

    A multistrategy approach to overcome the main challenges of nanoparticle-based solution-processed Cu2ZnSnSe4 thin film solar cells is presented. We developed an efficient ligand exchange strategy, using an antimony salt, to displace organic ligands from the surface of Cu2ZnSnS4 nanoparticles. An automated pulsed spray-deposition system was used to deposit the nanoparticles into homogeneous and crack-free films with controlled thickness. After annealing the film in a Se-rich atmosphere, carbon-free and crystalline Cu2ZnSnSe4 absorber layers were obtained. Not only was crystallization promoted by the complete removal of organics, but also Sb itself played a critical role. The Sb-assisted crystal growth is associated with the formation of a Sb-based compound at the grain boundaries, which locally reduces the melting point, thus promoting the film diffusion-limited crystallization.

  16. CC-chemokine receptor 7 and its ligand CCL19 promote mitral valve interstitial cell migration and repair.

    PubMed

    Wang, Xiaozhi; Wang, Liang; Miao, Liping; Zhao, Rong; Wu, Yanhu; Kong, Xiangqing

    2015-11-01

    The effect of CC-chemokine receptor 7 (CCR7) and CC-chemokine ligand 19 (CCL19) on rheumatic mitral stenosis is unknown. This study aimed to explore the roles of CCR7 and CCL19 in rheumatic mitral stenosis by measuring the expression of CCR7 and CCL19 in human mitral valves from rheumatic mitral stenosis patients. Additionally, we examined their effects on human mitral valve interstitial cells (hMVICs) proliferation, apoptosis and wound repair. CCR7 and CCL19 expression was measured in the mitral valves from rheumatic mitral stenosis patients (n = 10) and compared to normal mitral valves (n = 5). CCR7 was measured in cultured hMVICs from rheumatic mitral stenosis patients and normal donors by RT-PCR and immunofluorescence. The cells were also treated with exogenous CCL19, and the effects on wound healing, proliferation and apoptosis were assayed. In the rheumatic mitral valves, valve interstitial cells expressed CCR7, while mononuclear cells and the endothelium expressed CCL19. Healthy mitral valves did not stain positive for CCR7 or CCL19. CCR7 was also detected in cultured rheumatic hMVICs or in normal hMVICs treated with CCL19. In a wound healing experiment, wound closure rates of both rheumatic and normal hMVICs were significantly accelerated by CCL19. These effects were abrogated by a CCR7 neutralizing antibody. The CCR7/CCL19 axis did not influence the proliferation or apoptosis of hMVICs, indicating that wound healing was due to increased migration rates rather than increased proliferation. In conclusion, CCR7 and CCL19 were expressed in rheumatic mitral valves. The CCR7/CCL19 axis may regulate remodeling of rheumatic valve injury through promoting migratory ability of hMVICs.

  17. Tensile force on human macrophage cells promotes osteoclastogenesis through receptor activator of nuclear factor κB ligand induction.

    PubMed

    Kao, Chia-Tze; Huang, Tsui-Hsien; Fang, Hsin-Yuan; Chen, Yi-Wen; Chien, Chien-Fang; Shie, Ming-You; Yeh, Chia-Hung

    2016-07-01

    Little is known about the effects of tensile forces on osteoclastogenesis by human monocytes in the absence of mechanosensitive cells, including osteoblasts and fibroblasts. In this study we consider the effects of tensile force on osteoclastogenesis in human monocytes. The cells were treated with receptor activator of nuclear factor κB ligand (RANKL) to promote osteoclastogenesis. Then,expression and secretion of cathepsin K were examined. RANKL and the formation of osteoclasts during the osteoclast differentiation process under continual tensile stress were evaluated by Western blot. It was also found that -100 kPa or lower induces RANKL-enhanced tartrate-resistant acid phosphatase activity in a dose-dependent manner. Furthermore, an increased tensile force raises the expression and secretion of cathepsin K elevated by RANKL, and is concurrent with the increase of TNF-receptor-associated factor 6 induction and nuclear factor κB activation. Overall, the current report demonstrates that tensile force reinforces RANKL-induced osteoclastogenesis by retarding osteoclast differentiation. The tensile force is able to modify every cell through dose-dependent in vitro RANKL-mediated osteoclastogenesis, affecting the fusion of preosteoclasts and function of osteoclasts. However, tensile force increased TNF-receptor-associated factor 6 expression. These results are in vitro findings and were obtained under a condition of tensile force. The current results help us to better understand the cellular roles of human macrophage populations in osteoclastogenesis as well as in alveolar bone remodeling when there is tensile stress.

  18. Dissolution of Fe(III)(hydr) oxides by metal-EDTA complexes

    SciTech Connect

    Nowack, B.; Sigg, L. |

    1997-03-01

    The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA > CaEDTA > PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced. 35 refs., 11 figs., 4 tabs.

  19. Double hydrophosphination of alkynes promoted by rhodium: the key role of an N-heterocyclic carbene ligand.

    PubMed

    Di Giuseppe, Andrea; De Luca, Roberto; Castarlenas, Ricardo; Pérez-Torrente, Jesús J; Crucianelli, Marcello; Oro, Luis A

    2016-04-25

    The regioselective double hydrophosphination of alkynes mediated by rhodium catalysts is presented. The distinctive stereoelectronic properties of the NHC ligand prevent the catalyst deactivation by diphosphine coordination thereby allowing for the closing of a productive catalytic cycle.

  20. How a redox-innocent metal promotes the formal reductive elimination of biphenyl using redox-active ligands.

    PubMed

    Ashley, Daniel Charles; Baik, Mu-Hyun

    2015-03-01

    One of the most compelling strategies for utilizing redox-active ligands is to perform redox events at the ligands to avoid accessing prohibitively high energy oxidation states at the metal center. This has been demonstrated experimentally in many systems, yet there is little understanding of the fundamental electronic structures involved with these transformations or how to control them. Here, the reductive elimination of biphenyl from [M(isq)2Ph2] (M = Ti, Zr, and Hf and isq = 2,4-di-tert-butyl-6-tert-butyliminosemiquinone) was studied computationally. It was found that the metal remains in the +IV oxidation state and all redox chemistry was mediated by the redox-active ligands. Two types of electron-transfer mechanisms were identified, an asymmetric unpaired electron transfer (UET) and a symmetric pairwise electron transfer (PET), the former always being lower in energy. The energetic differences between these two mechanisms were explained through simple molecular orbital theory arguments. Despite the metal's redox-inactivity, it still has a marked influence on the calculated energetics of the reaction, with the Ti systems being much more reactive than the Zr/Hf systems. This primarily originates from the shorter Ti-Ph bond, which leads to a stronger filled-filled interaction between these ligands at the reactant state. This greater reactant destabilization leads to the lower activation energies.

  1. Iron(III) bound by hydrosulfide anion ligands: NO-promoted stabilization of the [Fe(III)-SH] motif.

    PubMed

    Tsou, Chih-Chin; Chiu, Wei-Chun; Ke, Chun-Hung; Tsai, Jia-Chun; Wang, Yun-Ming; Chiang, Ming-Hsi; Liaw, Wen-Feng

    2014-07-01

    Spontaneous transformation of the thermally stable [HS](-)-bound {Fe(NO)2}(9) dinitrosyl iron complex (DNIC) [(HS)2Fe(NO)2](-) (1) into [(NO)2Fe(μ-S)]2(2-) (Roussin's red salt (RRS)) along with release of H2S, probed by NBD-SCN (NBD = nitrobenzofurazan), was observed when DNIC 1 was dissolved in water at ambient temperature. The reversible transformation of RRS into DNIC 1 (RRS → DNIC 1) in the presence of H2S was demonstrated. In contrast, the thermally unstable hydrosulfide-containing mononitrosyl iron complex (MNIC) [(HS)3Fe(III)(NO)](-) (3) and [Fe(III)(SH)4](-) (5) in THF/DMF spontaneously dimerized into the first structurally characterized Fe(III)-hydrosulfide complexes [(NO)(SH)Fe(μ-S)]2(2-) (4) with two {Fe(NO)}(7) motifs antiferromagnetically coupled and [(SH)2Fe(μ-S)]2(2-) (6) resulting from two Fe(III) (S = 5/2) centers antiferromagnetically coupled to yield an S = 0 ground state with thermal occupancy of higher spin states, respectively. That is, the greater the number of NO ligands bound to [2Fe2S], the larger the antiferromagnetic coupling constant. On the basis of DFT computation and the experimental (and calculated) reduction potential (E1/2) of complexes 1, 3, and 5, the NO-coordinate ligand(s) of complexes 1 and 3 serves as the stronger electron-donating ligand, compared to thiolate, to reduce the effective nuclear charge (Zeff) of the iron center and prevent DNIC 1 from dimerization in an organic solvent (MeCN).

  2. An activin receptor IIA ligand trap promotes erythropoiesis resulting in a rapid induction of red blood cells and haemoglobin

    PubMed Central

    Carrancio, Soraya; Markovics, Jennifer; Wong, Piu; Leisten, Jim; Castiglioni, Paola; Groza, Matthew C; Raymon, Heather K; Heise, Carla; Daniel, Tom; Chopra, Rajesh; Sung, Victoria

    2014-01-01

    Sotatercept (ACE-011), a recombinant human fusion protein containing the extracellular domain of the human Activin receptor IIA, binds to and inhibits activin and other members of the transforming growth factor -β (TGF-β) superfamily. Administration of sotatercept led to a rapid and sustained increase in red blood cell (RBC) count and haemoglobin (Hb) in healthy volunteers (phase I clinical trials), but the mechanism is not fully understood. Mice treated with RAP-011 (murine ortholog of ACE-011) respond with a rapid (within 24 h) increase in haematocrit, Hb, and RBC count. These effects are accompanied by an equally rapid stimulation of late-stage erythroid precursors in the bone marrow (BM). RAP-011 also induces a significant increase in erythroid burst-forming units and erythropoietin, which could contribute to additional, sustained effects on RBC production. Further in vitro co-culture studies demonstrate that BM accessory cells are required for RAP-011 effects. To better understand which TGF-β family ligand(s) mediate RAP-011 effects, we evaluated the impact of several of these ligands on erythroid differentiation. Our data suggest that RAP-011 may act to rescue growth differentiation factor 11/Activin A-induced inhibition of late-stage erythropoiesis. These data define the mechanism of action of a novel agent that regulates RBC differentiation and provide the rationale to develop sotatercept for the treatment of anaemia and ineffective erythropoiesis. PMID:24635723

  3. Dissolution of iron(III)(HYDR)oxides by metal-EDTA-complexes

    SciTech Connect

    Nowack, B.; Sigg, L.

    1996-10-01

    The dissolution of Fe(III)(hydroxides) (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by adsorption of the metal-EDTA to the surface, dissociation of the complex at the surface and release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to uncomplexed EDTA. The rate decreases in the order EDTA >> CaEDTA > PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the system: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step (1) is more important than (2) and the difference in the dissolution rate for several metals is small. In the case of hydrous ferric oxide, step (2) is rate-limiting and the effect of the complexed metal is very pronounced.

  4. Evidence that estrogen receptor beta enhances MMP-13 promoter activity in HIG-82 cells and that this enhancement can be influenced by ligands and involves specific promoter sites.

    PubMed

    Lu, Ting; Achari, Yamini; Rattner, Jerome B; Hart, David A

    2007-06-01

    Degradation of articular cartilage is characteristic of osteoarthritis, and matrix metalloproteinase-13 (MMP-13) has been implicated in this condition. Estrogen receptors (ERs) are present in connective tissues, indicating these tissues' potential responsiveness to estrogen. We based this study on the hypothesis that estrogen receptor beta (ERbeta) can modulate MMP-13 promoter activity. Transfection of cells with ERbeta constructs led to the induction of the endogenous MMP-13 gene, as evidenced by increased mRNA levels. The results also indicated that MMP-13 promoter construct activity in the HIG-82 cell line significantly increased when ERbeta was present, and that estrogen downregulated this response in a dose-dependent manner. ERbeta was shown to enhance MMP-13 expression somewhat more strongly than ERalpha, and the impact of a number of selective ER modulators (tamoxifen, raloxifene, and ICI 182,780) on ERbeta enhancement of promoter activity was found to be significantly less than that of estrogen. Furthermore, transcription regulatory sites in the MMP-13 promoter, specifically AP-1 and PEA-3, were shown to act in conjunction to mediate ERbeta effects. Thus, ERbeta likely influences MMP-13 promoter expression in normal and disease processes.

  5. A study of promoter and intronic markers of ApoI/Fas gene and the interaction with Fas ligand in relapsing multiple sclerosis.

    PubMed

    Lucas, Miguel; Zayas, María D; De Costa, Alzenira F; Solano, Francisca; Chadli, Amal; Dinca, Luminita; Izquierdo, Guillermo

    2004-01-01

    We studied the association between multiple sclerosis (MS) and a novel single nucleotide polymorphism (SNP), A/T(735)G/C, localized in intron IV of the ApoI/Fas gene, which is recognized by the restrictase MaeI. Fas-MaeI genotypes were screened in chromosomes of 215 healthy individuals and 312 relapsing MS patients of Spanish extraction. We also analyzed the interaction of this new intragenic marker with others previously associated with MS: class II HLA-DRB1*1501, Fas-MvaI and Fas ligand. The distribution of Fas-MaeI genotypes was in equilibrium in the control cohort, while a significant disequilibrium was observed in the patient group (chi(2) = 16; p = 0.0003). Fas-MaeI genotypes were statistically different in the MS and control groups, but the allele frequencies were not. Sharing of MvaI/MaeI genotypes of the promoter/intron IV region did not differ between patients and controls. We failed to find different frequencies of ApoI/Fas genotypes in the population of MS carriers of the class II HLA-DRB1*1501 allele. The case/control comparative study showed a relative risk (OR close to 1.6) of MS in individuals harboring the T and A alleles of Fas- MaeI and Fas ligand, respectively. In conclusion, our findings suggest a weak association between the intronic marker Fas-MaeI and MS and a relative interaction with Fas ligand in an MS cohort of South Spanish extraction.

  6. A point mutation in the extracellular domain of KIT promotes tumorigenesis of mast cells via ligand-independent auto-dimerization

    PubMed Central

    Amagai, Yosuke; Matsuda, Akira; Jung, Kyungsook; Oida, Kumiko; Jang, Hyosun; Ishizaka, Saori; Matsuda, Hiroshi; Tanaka, Akane

    2015-01-01

    Mutations in the juxtamembrane and tyrosine kinase domains of the KIT receptor have been implicated in several cancers and are known to promote tumorigenesis. However, the pathophysiological manifestations of mutations in the extracellular domain remain unknown. In this study, we examined the impact of a mutation in the extracellular domain of KIT on mast cell tumorigenesis. A KIT mutant with an Asn508Ile variation (N508I) in the extracellular domain derived from a canine mast cell tumor was introduced into IC-2 cells. The IC-2N508I cells proliferated in a cytokine-independent manner and showed KIT auto-phosphorylation. Subcutaneous injection of IC-2N508I cells into the dorsal area of immunodeficient BALB/c-nu/nu mice resulted in the formation of solid tumors, but tumor progression was abrogated by treatment with a tyrosine kinase inhibitor (STI571). In addition, the N508I mutant KIT protein dimerized in the absence of the natural ligand, stem cell factor. Structure modeling indicates that the increased hydrophobicity of the mutant led to the stabilization of KIT dimers. These results suggest that this extracellular domain mutation confers a ligand-independent tumorigenic phenotype to mast cells by KIT auto-dimerization that is STI571-sensitive. This is the first report demonstrating the tumorigenic potential of a mutation in the extracellular domain of KIT. PMID:25965812

  7. A Novel AP-1 Element in the CD95 Ligand Promoter Is Required for Induction of Apoptosis in Hepatocellular Carcinoma Cells upon Treatment with Anticancer Drugs

    PubMed Central

    Eichhorst, Sören T.; Müller, Martina; Li-Weber, Min; Schulze-Bergkamen, Henning; Angel, Peter; Krammer, Peter H.

    2000-01-01

    The CD95 (also called APO-1 or Fas) system plays a major role in the induction of apoptosis in lymphoid and nonlymphoid tissues in response to a variety of extracellular signals, including chemotherapeutic drugs. Here we report that the CD95 ligand (CD95L) is upregulated in hepatoma cells upon treatment with antineoplastic drugs. Upregulation by different chemotherapeutic drugs is functionally relevant for drug-induced apoptosis and is mediated by transcriptional mechanisms. The MEKK1/JNKK pathway and a novel AP-1 element in the CD95L promoter downstream of the TATA box are required for CD95L upregulation. Thus, understanding the mechanisms of CD95-mediated apoptosis through CD95L upregulation upon treatment of hepatocellular carcinomas with chemotherapeutic drugs may contribute to the improvement of anticancer chemotherapy. PMID:11003676

  8. Binding of the Lactococcal Drug Dependent Transcriptional Regulator LmrR to Its Ligands and Responsive Promoter Regions

    PubMed Central

    van der Berg, Jan Pieter; Madoori, Pramod Kumar; Komarudin, Amalina Ghaisani; Thunnissen, Andy-Mark; Driessen, Arnold J. M.

    2015-01-01

    The heterodimeric ABC transporter LmrCD from Lactococcus lactis is able to extrude several different toxic compounds from the cell, fulfilling a role in the intrinsic and induced drug resistance. The expression of the lmrCD genes is regulated by the multi-drug binding repressor LmrR, which also binds to its own promoter to autoregulate its own expression. Previously, we reported the crystal structure of LmrR in the presence and absence of the drugs Hoechst 33342 and daunomycin. Analysis of the mechanism how drugs control the repressor activity of LmrR is impeded by the fact that these drugs also bind to DNA. Here we identified, using X-ray crystallography and fluorescence, that riboflavin binds into the drug binding cavity of LmrR, adopting a similar binding mode as Hoechst 33342 and daunomycin. Microscale thermophoresis was employed to quantify the binding affinity of LmrR to its responsive promoter regions and to evaluate the cognate site of LmrR in the lmrCD promoter region. Riboflavin reduces the binding affinity of LmrR for the promoter regions. Our results support a model wherein drug binding to LmrR relieves the LmrR dependent repression of the lmrCD genes. PMID:26267906

  9. cpg15 and cpg15-2 constitute a family of activity-regulated ligands expressed differentially in the nervous system to promote neurite growth and neuronal survival.

    PubMed

    Fujino, Tadahiro; Wu, Zhen; Lin, Walter C; Phillips, Marnie A; Nedivi, Elly

    2008-04-10

    Many ligands that affect nervous system development are members of gene families that function together to coordinate the assembly of complex neural circuits. cpg15/neuritin encodes an extracellular ligand that promotes neurite growth, neuronal survival, and synaptic maturation. Here we identify cpg15-2 as the only paralogue of cpg15 in the mouse and human genome. Both genes are expressed predominantly in the nervous system, where their expression is regulated by activity. cpg15-2 expression increases by more than twofold in response to kainate-induced seizures and nearly fourfold in the visual cortex in response to 24 hours of light exposure following dark adaptation. cpg15 and cpg15-2 diverge in their spatial and temporal expression profiles. cpg15-2 mRNA is most abundant in the retina and the olfactory bulb, as opposed to the cerebral cortex and the hippocampus for cpg15. In the retina, they differ in their cell-type specificity. cpg15 is expressed in retinal ganglion cells, whereas cpg15-2 is predominantly in bipolar cells. Developmentally, onset of cpg15-2 expression is delayed compared with cpg15 expression. CPG15-2 is glycosylphosphatidylinositol (GPI) anchored to the cell membrane and, like CPG15, can be released in a soluble-secreted form, but with lower efficiency. CPG15 and CPG15-2 were found to form homodimers and heterodimers with each other. In hippocampal explants and dissociated cultures, CPG15 and CPG15-2 promote neurite growth and neuronal survival with similar efficacy. Our findings suggest that CPG15 and CPG15-2 perform similar cellular functions but may play distinct roles in vivo through their cell-type- and tissue-specific transcriptional regulation. PMID:18265009

  10. Continuous plutonium dissolution apparatus

    DOEpatents

    Meyer, F.G.; Tesitor, C.N.

    1974-02-26

    This invention is concerned with continuous dissolution of metals such as plutonium. A high normality acid mixture is fed into a boiler vessel, vaporized, and subsequently condensed as a low normality acid mixture. The mixture is then conveyed to a dissolution vessel and contacted with the plutonium metal to dissolve the plutonium in the dissolution vessel, reacting therewith forming plutonium nitrate. The reaction products are then conveyed to the mixing vessel and maintained soluble by the high normality acid, with separation and removal of the desired constituent. (Official Gazette)

  11. Tunable DNA cleavage activity promoted by copper(ii) ternary complexes with N-donor heterocyclic ligands.

    PubMed

    Bortolotto, T; Silva-Caldeira, P P; Pich, C T; Pereira-Maia, E C; Terenzi, H

    2016-06-01

    Several small molecules have the capacity to cleave DNA promptly at high yields, even under mild conditions. Usually, this activity has no constraints, occurring without external or user control. Here, we demonstrate that UV-light exposure can greatly enhance the DNA cleavage activity promoted by four ternary copper(ii) complexes. A remarkable photocontrolled activity was achieved, which may be interesting for chemical and biochemical applications. PMID:27168172

  12. Arsenic Induced Phytate Exudation, and Promoted FeAsO4 Dissolution and Plant Growth in As-Hyperaccumulator Pteris vittata.

    PubMed

    Liu, Xue; Fu, Jing-Wei; Guan, Dong-Xing; Cao, Yue; Luo, Jun; Rathinasabapathi, Bala; Chen, Yanshan; Ma, Lena Q

    2016-09-01

    Arsenic hyperaccumulator Pteris vittata (PV) is efficient in taking up As and nutrients from As-contaminated soils. We evaluated the mechanisms used by PV to mobilize As and Fe by examining the impacts of As and root exudates on FeAsO4 solubilization, and As and Fe uptake in four plants: As-hyperaccumulators PV and Pteris multifida (PM), nonhyperaccumulator Pteris ensiformis (PE), and angiosperm plant tomato (Solanum lycopersicum). Phytate and oxalate were dominant in fern plants (>93%), which were 50-83, 15-42, and 0-32 mg kg(-1) phytate and 10-15, 7-26, and 4-12 mg kg(-1) oxalate for PV, PM, and PE respectively, with higher As inducing greater phytate exudation and no phytate being detected in tomato exudates. PV treated with phytate+FeAsO4 had higher As and Fe contents and larger biomass than phytate or FeAsO4 treatment, which were 340 vs 20 and 130 mg kg(-1) As in the fronds and 7900 vs 1600 and 4100 mg kg(-1) Fe in the roots. We hypothesized that As-induced phytate exudation helped PV to take up Fe and As from insoluble FeAsO4 and promoted PV growth. Our study suggests that phytate exudation may be special to fern plants, which may play an important role in enhancing As and nutrient uptake by plants, thereby increasing their efficiency in phytoremediation of As-contaminated soils. PMID:27483027

  13. Nickel/lanthanide single-molecule magnets: {Ni(3)Ln} "stars" with a ligand derived from the metal-promoted reduction of di-2-pyridyl ketone under solvothermal conditions.

    PubMed

    Efthymiou, Constantinos G; Stamatatos, Theocharis C; Papatriantafyllopoulou, Constantina; Tasiopoulos, Anastasios J; Wernsdorfer, Wolfgang; Perlepes, Spyros P; Christou, George

    2010-11-01

    Unusual {Ni(II)(3)Ln(III)(μ-OR)(6)}(3+) complexes with a "star" topology have been prepared with ligands derived from the metal-promoted reduction of di-2-pyridyl ketone under solvothermal conditions; the Dy(III) member shows weak single-molecule-magnet behavior.

  14. Unemployment and marital dissolution.

    PubMed

    Jensen, P; Smith, N

    1990-01-01

    "This paper analyses the effects of unemployment on the probability of marital dissolution. Based on panel data for a sample of Danish married couples, we estimate a dynamic model for the probability of marital dissolution where we take into account the possible effects of unemployment for both spouses. We also control for other factors such as education, age, presence of children, place of residence, health and economic factors. The empirical results show that unemployment seems to be an important factor behind marital instability. However, only unemployment of the husband has an effect, and this effect is immediate." PMID:12283481

  15. [Separation and determination of optical isomers of phenylephrine by chiral ligand exchange capillary elcctrophoresis coupling with the promoting effect of ionic liquid].

    PubMed

    Yang, Simei; Zhang, Jiayao; Li, Fei; Hu, Xufang; Cao, Qiue

    2016-01-01

    A method for the separation and determination of optical isomers of phenylephrine was developed based on the promoting effect of non-chiral ionic liquid on chiral ligand-exchange capillary electrophoresis after the electrophoretic parameters were optimized systematically. R-phenylephrine and S-phenylephrine can be separated and determined effectively in 20 mmol/L Tris-H3PO4 buffer solution (pH 5.4) composed of 4.0 mmol/L Cu(II), 8.0 mmol/L L-proline (L-Pro) and 15 mmol/L 1-butyl-3-methylimidazolium chloride ([BMIM] Cl) with the applied voltage of 20 kV, capillary temperature of 25 °C , detection wavelength of 254 nm, and injection of 5 s at 3,447 Pa. The resolution of R- and S-phenylephrines was 1. 42. The linear ranges for the determination of R-phenylephrine and S-phenylephrine were 12. 5 - 150 mg/L and 15. 0-150 mg/L, respectively. The method has been satisfactorily used for the determination of R-phenylephrine and S-phenylephrine in the spiked blood and urine samples. The spiked recoveries in the urine sample were in the range of 93. 7% -108. 2% with the RSDs lower than 3. 18% (n= 3) , and the spiked recoveries in the blood sample were in the range of 91. 4% and 113. 1% with the RSDs lower than 4. 82% (n =3).

  16. [Separation and determination of optical isomers of phenylephrine by chiral ligand exchange capillary elcctrophoresis coupling with the promoting effect of ionic liquid].

    PubMed

    Yang, Simei; Zhang, Jiayao; Li, Fei; Hu, Xufang; Cao, Qiue

    2016-01-01

    A method for the separation and determination of optical isomers of phenylephrine was developed based on the promoting effect of non-chiral ionic liquid on chiral ligand-exchange capillary electrophoresis after the electrophoretic parameters were optimized systematically. R-phenylephrine and S-phenylephrine can be separated and determined effectively in 20 mmol/L Tris-H3PO4 buffer solution (pH 5.4) composed of 4.0 mmol/L Cu(II), 8.0 mmol/L L-proline (L-Pro) and 15 mmol/L 1-butyl-3-methylimidazolium chloride ([BMIM] Cl) with the applied voltage of 20 kV, capillary temperature of 25 °C , detection wavelength of 254 nm, and injection of 5 s at 3,447 Pa. The resolution of R- and S-phenylephrines was 1. 42. The linear ranges for the determination of R-phenylephrine and S-phenylephrine were 12. 5 - 150 mg/L and 15. 0-150 mg/L, respectively. The method has been satisfactorily used for the determination of R-phenylephrine and S-phenylephrine in the spiked blood and urine samples. The spiked recoveries in the urine sample were in the range of 93. 7% -108. 2% with the RSDs lower than 3. 18% (n= 3) , and the spiked recoveries in the blood sample were in the range of 91. 4% and 113. 1% with the RSDs lower than 4. 82% (n =3). PMID:27319173

  17. Mergers, Annexations, Dissolutions

    ERIC Educational Resources Information Center

    Russo, Alexander

    2006-01-01

    Consolidations come in all shapes and sizes, including mergers, annexations and dissolutions. They do not all take place under state mandate, however. A handful of districts consolidate every year in some states like Illinois that have large numbers of small districts, many of them dual districts that serve K-8 or 9-12 in the same geographic area.…

  18. HEPA filter dissolution process

    DOEpatents

    Brewer, K.N.; Murphy, J.A.

    1994-02-22

    A process is described for dissolution of spent high efficiency particulate air (HEPA) filters and then combining the complexed filter solution with other radioactive wastes prior to calcining the mixed and blended waste feed. The process is an alternate to a prior method of acid leaching the spent filters which is an inefficient method of treating spent HEPA filters for disposal. 4 figures.

  19. Hepa filter dissolution process

    DOEpatents

    Brewer, Ken N.; Murphy, James A.

    1994-01-01

    A process for dissolution of spent high efficiency particulate air (HEPA) filters and then combining the complexed filter solution with other radioactive wastes prior to calcining the mixed and blended waste feed. The process is an alternate to a prior method of acid leaching the spent filters which is an inefficient method of treating spent HEPA filters for disposal.

  20. Distinctive Reactivities at Biotite Edge and Basal Planes in the Presence of Organic Ligands: Implications for Organic-Rich Geologic CO2 Sequestration.

    PubMed

    Zhang, Lijie; Jun, Young-Shin

    2015-08-18

    To better understand how scCO2-saturated brine-mineral interactions can affect safe and efficient geologic CO2 sequestration (GCS), we studied the effects of organic ligands (acetate and oxalate) on biotite dissolution and surface morphological changes. The experimental conditions were chosen to be relevant to GCS sites (95 °C and 102 atm CO2). Quantitative analyses of dissolution differences between biotite edge and basal planes were made. Acetate slightly inhibited biotite dissolution and promoted secondary precipitation. The effect of acetate was mainly pH-induced aqueous acetate speciation and the subsequent surface adsorption. Under the experimental conditions, most of acetate exists as acetic acid and adsorbs to biotite surface Si and Al sites, thereby reducing their release. However, oxalate strongly enhanced biotite dissolution and induced faster and more significant surface morphology changes by forming bidentate mononuclear surface complexes. For the first time, we show that oxalate selectively attacks edge surface sites and enhances biotite dissolution. Thus, oxalate increases the relative reactivity ratio of biotite edge surfaces to basal surfaces, while acetate does not impact this relative reactivity. This study provides new information on reactivity differences at biotite edge and basal planes in the presence of organic ligands, which has implications for safe CO2 storage in organic-rich sites.

  1. Determinants of marriage dissolution

    NASA Astrophysics Data System (ADS)

    Rahim, Mohd Amirul Rafiq Abu; Shafie, Siti Aishah Mohd; Hadi, Az'lina Abdul; Razali, Nornadiah Mohd; Azid @ Maarof, Nur Niswah Naslina

    2015-10-01

    Nowadays, the number of divorce cases among Muslim couples is very worrisome whereby the total cases reported in 2013 increased by half of the total cases reported in the previous year. The questions on the true key factors of dissolution of marriage continue to arise. Thus, the objective of this study is to reveal the factors that contribute to the dissolution of marriage. A total of 181 cases and ten potential determinants were included in this study. The potential determinants considered were age at marriage of husband and wife, educational level of husband and wife, employment status of husband and wife, income of husband and wife, the number of children and the presence at a counseling session. Logistic regression analysis was used to analyze the data. The findings revealed that four determinants, namely the income of husband and wife, number of children and the presence at a counselling session were significant in predicting the likelihood of divorce among Muslim couples.

  2. Fms-related tyrosine kinase 3 ligand promotes proliferation of placenta amnion and chorion mesenchymal stem cells in vitro.

    PubMed

    Li, Fang; Xu, Yunyun; Xu, Xiaoxia; Xu, Biao; Zhao, Juan; Zhang, Xueguang

    2014-07-01

    Placental mesenchymal stem cells (PMSCs) have important biological properties and the potential for application in numerous clinical fields, including hematopoietic stem cell transplantation and myocardial repair. There are two types of MSCs in the placenta, amniotic mesenchymal stem cells (AMSCs) and chorion mesenchymal stem cells (CMSCs). By comparing the biological characteristics of human placental AMSCs with CMSCs, the present study identified that CD90‑ and CD166‑positive cells were located in the amniotic stroma and chorion stroma surrounding the vessels. In addition, the cultured AMSCs and CMSCs expressed high levels of CD73, CD90, CD105, CD29 and CD44; however they did not express CD14, CD34, CD45 and HLA-DR. Furthermore, the amplification of the fms-related tyrosine kinase 3 ligand (FL) in AMSCs and CMSCs was investigated in vitro. The results demonstrated that FL is able to promote the proliferation of AMSCs and CMSCs effectively in vitro, particularly that of CMSCs. In the FL group, the phenotype and the ability of AMSCs and CMSCs to differentiate into mesenchymal lineages did not change. Flt3, the receptor of FL, is expressed in AMSCs and CMSCs. In conclusion, mesenchymal stem cells with low immunogenicity were identified in the placental amniotic membrane and around the chorion axis. Furthermore, FL has a positive effect on the proliferation of AMSCs and CMSCs in vitro; however, does not affect their differentiation potential. It is particularly promising that FL is able to stimulate CMSCs to proliferate in vitro.

  3. Enhanced dissolution of basaltic glass in brackish waters: Impact on biogeochemical cycles

    NASA Astrophysics Data System (ADS)

    Morin, Guillaume P.; Vigier, Nathalie; Verney-Carron, Aurélie

    2015-05-01

    In order to better constrain the geochemical budget of Si in the ocean, and potentially other elements released by the dissolution of silicates, the alteration of riverine particulate material in estuaries and seawater needs to be estimated. For this, a series of alteration experiments of basaltic glass were performed at various degrees of salinity (from 0 to 3.5 g L-1) in far-from-equilibrium conditions. The solution used is a filtered natural seawater standard from the Atlantic Ocean. The forward dissolution rates increase from 2.1 ṡ10-7 molSim-2s-1 (S = 0 gL-1) to 7.7 ṡ10-7 molSim-2s-1 (S = 3.5 gL-1) at 90 °C and were extrapolated at 16 °C (from 2.9 ṡ10-10 molSim-2s-1 at S = 0 gL-1 to 1.1 ṡ10-9 molSim-2s-1 at S = 3.5 gL-1). This positive relationship between glass dissolution rate and salinity degree is consistent with published investigations concerning the role of specific cations and ligands present in seawater, which can promote dissolution at the glass surface. These results illustrate the potential of river basaltic glass particles to dissolve quickly in the water column after entering into the brackish waters of estuaries, and before sinking on continental margins. Based on these dissolution rates and on assumptions on the particulate solid flux of fresh basaltic glass exported by rivers towards the ocean, the corresponding flux of dissolved Si is estimated to range between 2 and 8 ṡ1012 molSiyr-1. This is of the same order of magnitude as the estimated river dissolved Si flux, which represents therefore a significant input of Si into the ocean. Additionally, if the glass dissolution process remains congruent during the residence time of suspended particles into the water column, the K flux to the ocean could also be significantly affected.

  4. Solubility limits on radionuclide dissolution

    SciTech Connect

    Kerrisk, J.F.

    1984-12-31

    This paper examines the effects of solubility in limiting dissolution rates of a number of important radionuclides from spent fuel and high-level waste. Two simple dissolution models were used for calculations that would be characteristics of a Yucca Mountain repository. A saturation-limited dissolution model, in which the water flowing through the repository is assumed to be saturated with each waste element, is very conservative in that it overestimates dissolution rates. A diffusion-limited dissolution model, in which element-dissolution rates are limited by diffusion of waste elements into water flowing past the waste, is more realistic, but it is subject to some uncertainty at this time. Dissolution rates of some elements (Pu, Am, Sn, Th, Zr, Sm) are always limited by solubility. Dissolution rates of other elements (Cs, Tc, Np, Sr, C, I) are never solubility limited; their release would be limited by dissolution of the bulk waste form. Still other elements (U, Cm, Ni, Ra) show solubility-limited dissolution under some conditions. 9 references, 3 tables.

  5. Mathematical modeling of precipitation and dissolution reactions in microbiological systems.

    PubMed

    Rittmann, Bruce E; Banaszak, James E; VanBriesen, Jeanne M; Reed, Donald T

    2002-01-01

    We expand the biogeochemical model CCBATCH to include a precipitation/dissolution sub-model that contains kinetic and equilibrium options. This advancement extends CCBATCH's usefulness to situations in which microbial reactions cause or are affected by formation or dissolution of a solid phase. The kinetic option employs a rate expression that explicitly includes the intrinsic kinetics for reaction or mass-transport control, the difference from thermodynamic equilibrium, and the aqueous concentration of the rate-limiting metal or ligand. The equilibrium feature can be used alone, and it also serves as check that the kinetic rate never is too fast and "overshoots" equilibrium. The features of the expanded CCBATCH are illustrated by an example in which the precipitation of Fe(OH)3(s) allows the biodegradation of citric acid, even though complexes are strong and not bioavailable. Precipitation releases citrate ligand, and biodegradation of the citrate increases the pH.

  6. Plutonium dissolution process

    DOEpatents

    Vest, M.A.; Fink, S.D.; Karraker, D.G.; Moore, E.N.; Holcomb, H.P.

    1994-01-01

    A two-step process for dissolving Pu metal is disclosed in which two steps can be carried out sequentially or simultaneously. Pu metal is exposed to a first mixture of 1.0-1.67 M sulfamic acid and 0.0025-0.1 M fluoride, the mixture having been heated to 45-70 C. The mixture will dissolve a first portion of the Pu metal but leave a portion of the Pu in an oxide residue. Then, a mineral acid and additional fluoride are added to dissolve the residue. Alternatively, nitric acid between 0.05 and 0.067 M is added to the first mixture to dissolve the residue as it is produced. Hydrogen released during the dissolution is diluted with nitrogen.

  7. Plutonium dissolution process

    DOEpatents

    Vest, Michael A.; Fink, Samuel D.; Karraker, David G.; Moore, Edwin N.; Holcomb, H. Perry

    1996-01-01

    A two-step process for dissolving plutonium metal, which two steps can be carried out sequentially or simultaneously. Plutonium metal is exposed to a first mixture containing approximately 1.0M-1.67M sulfamic acid and 0.0025M-0.1M fluoride, the mixture having been heated to a temperature between 45.degree. C. and 70.degree. C. The mixture will dissolve a first portion of the plutonium metal but leave a portion of the plutonium in an oxide residue. Then, a mineral acid and additional fluoride are added to dissolve the residue. Alteratively, nitric acid in a concentration between approximately 0.05M and 0.067M is added to the first mixture to dissolve the residue as it is produced. Hydrogen released during the dissolution process is diluted with nitrogen.

  8. Organic Ligand Enhanced Cr(VI) Treatment in Pyrite Permeable Reactive Barriers

    NASA Astrophysics Data System (ADS)

    Kantar, Cetin; Ari, Cihan; Samet Bulbul, Muhammet

    2014-05-01

    Permeable reactive barriers (PRB), installed in subsurface in the path of flowing groundwater can offer a viable option for in situ remediation of Cr(VI)-contaminated subsurface systems. In this study, batch and column experiments were performed to determine the effects of organic ligands (L) on Cr(VI) treatment in PRBs containing pyrite. The organic ligands used include citrate, tartrate, oxalate, EDTA and salycilate. The results indicate that in the absence of organic ligands, the Cr(VI)removal by pyrite occurred only under acidic conditions (e.g., pH > 5). However, organic ligands led to a significant increase in Cr(VI) removal with pyrite depending on the type of organic ligand used, Cr(VI)/LT ratio and water chemistry (e.g., pH). While salicylate had no effect on Cr(VI) removal relative to non-ligand systems, the organic ligands including citrate, tartrate and oxalate significantly improved Cr(VI) removal under acidic to alkaline pH range. On the other hand, EDTA only improved Cr(VI) removal by pyrite under alkaline pH conditions relative to non-ligand conditions. In general, the efficiency of organic ligands on Cr(VI) removal decreased in the order: citrate > tartrate> oxalate>EDTA>salycilate. The X-ray photoelectron spectroscopy (XPS) and zeta potential measurements suggest that the Cr(VI) removal by pyrite occured due to the reduction of Cr(VI) to Cr(III), coupled with the oxidation of Fe(II) to Fe(III) and disulfide (S22-) to sulfate (SO42-) at the pyrite surface as well as in aqueous phase. However, the precipitation of sparingly soluble Fe(III-Cr(III)(oxy) hydroxide phases on pyrite surface led to surface passivation, which, then, inhibited further Cr(VI) reduction. The addition of organic ligands increased Cr(VI) reduction by pyrite due to: 1) the removal of the surface oxidation products by forming highly soluble Cr(III) and Fe(III)-ligand complexes as well as 2) the ligand promoted dissolution of Fe(II) from pyrite, which, subsequently, reduced Cr

  9. A Dinuclear Ruthenium-Based Water Oxidation Catalyst: Use of Non-Innocent Ligand Frameworks for Promoting Multi-Electron Reactions

    PubMed Central

    Laine, Tanja M; Kärkäs, Markus D; Liao, Rong-Zhen; Siegbahn, Per E M; Åkermark, Björn

    2015-01-01

    Insight into how H2O is oxidized to O2 is envisioned to facilitate the rational design of artificial water oxidation catalysts, which is a vital component in solar-to-fuel conversion schemes. Herein, we report on the mechanistic features associated with a dinuclear Ru-based water oxidation catalyst. The catalytic action of the designed Ru complex was studied by the combined use of high-resolution mass spectrometry, electrochemistry, and quantum chemical calculations. Based on the obtained results, it is suggested that the designed ligand scaffold in Ru complex 1 has a non-innocent behavior, in which metal–ligand cooperation is an important part during the four-electron oxidation of H2O. This feature is vital for the observed catalytic efficiency and highlights that the preparation of catalysts housing non-innocent molecular frameworks could be a general strategy for accessing efficient catalysts for activation of H2O. PMID:25925847

  10. Mechanical clot dissolution: new concept.

    PubMed

    Bildsoe, M C; Moradian, G P; Hunter, D W; Castaneda-Zuniga, W R; Amplatz, K

    1989-04-01

    The authors present preliminary data on in vitro mechanical clot dissolution by means of a catheter with a tiny high-speed propeller enclosed in a special housing. Preweighed human blood clots were subjected to the catheter in a test tube with saline at various propeller speeds and durations of application. After filtration of the resultant slurry, the clot residue was weighed and examined histologically. Clot dissolution was found to be related to both the duration and speed of propeller rotation. No fibrin residue was seen after dissolution, although potential embolic material, composed of clumps of cellular debris as large as 208 microns in longest dimension, was found. Mechanical clot dissolution could possibly be used in any natural or synthetic blood vessel in which there is acute or subacute thrombosis, with fewer complications and lower cost than obtained with traditional methods.

  11. Alunite dissolution rates: Dissolution mechanisms and implications for Mars

    NASA Astrophysics Data System (ADS)

    Miller, J. L.; Elwood Madden, A. S.; Phillips-Lander, C. M.; Pritchett, B. N.; Elwood Madden, M. E.

    2016-01-01

    Alunite (KAl3(SO4)2(OH)6) is a hydrated aluminous sulfate mineral associated with acidic, oxidizing aqueous environments on Earth. Additionally, orbiting spacecraft and rovers on Mars have reported spectral data that indicate a range of mono- and polyhydrated sulfate phases and hydroxysulfate phases, suggesting such conditions also existed on Mars in the past. This study examines alunite dissolution rates in aqueous systems with varying pH, temperature, and solution chemistry conditions. Alunite dissolution rates in dilute solutions are 2-3 orders of magnitude slower than jarosite dissolution rates measured under analogous conditions. Similar to jarosite, alunite dissolution rates vary as a function of activity of H+ and OH- following the rate law log r (mol m-2 s-1) = -0.133(±0.02)pH - 10.65(±0.07) at pH < 5 and log r = 0.194(±0.04)pH - 12.53(±0.26) at pH > 5. However, minimum alunite dissolution rates are shifted to higher pH (5-5.5), likely due to differences in Fe and Al speciation. Alunite and jarosite rates converge in saturated NaCl and CaCl2 brines as the activity of water decreases, suggesting that differences in water exchange rates with Fe3+ and Al3+ control dissolution rates in dilute solutions, while metal-Cl- complexation occurs at similar rates within the brines. Particle lifetimes based on measured dissolution rates in dilute solutions show that alunite particles are expected to be preserved two orders of magnitude longer than jarosite particles over a range of pH and temperature conditions. In particular, alunite is more likely to be preserved in neutral to moderately alkaline systems compared to jarosite, which is expected to be preserved in more acidic conditions. Alunite dissolution produced amorphous Al-rich alteration products at moderate to high pH. Unlike jarosite, alunite dissolution does not show a clear trend as a function of temperature; alunite dissolution rates do not increase with increasing temperature, likely due to lower

  12. 50 CFR 270.23 - Dissolution of Councils.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 50 Wildlife and Fisheries 11 2013-10-01 2013-10-01 false Dissolution of Councils. 270.23 Section 270.23 Wildlife and Fisheries NATIONAL MARINE FISHERIES SERVICE, NATIONAL OCEANIC AND ATMOSPHERIC ADMINISTRATION, DEPARTMENT OF COMMERCE FISH AND SEAFOOD PROMOTION SPECIES-SPECIFIC SEAFOOD MARKETING...

  13. The mouse CCR2 gene is regulated by two promoters that are responsive to plasma cholesterol and peroxisome proliferator-activated receptor {gamma} ligands

    SciTech Connect

    Chen Yiming; Green, Simone R.; Ho, Jessica; Li, Andrew; Almazan, Felizidad; Quehenberger, Oswald . E-mail: oquehenberger@ucsd.edu

    2005-06-24

    We have previously shown that the expression of monocyte CCR2, the receptor for monocyte chemoattractant protein-1, is induced by plasma cholesterol. The present study examines the mechanisms that regulate monocyte CCR2 expression in hypercholesterolemia using a mouse model. Our data demonstrate that in the mouse, CCR2 expression in circulating monocytes is controlled by two promoters P1 and P2. The two distinct transcripts, which encode the same protein, are produced by alternative splicing in the 5'-untranslated region. Both promoters are constitutively active, but only P2 is stimulated by cholesterol. However, both promoters are repressed by peroxisome proliferator-activated receptor {gamma}.

  14. FAM19A4 is a novel cytokine ligand of formyl peptide receptor 1 (FPR1) and is able to promote the migration and phagocytosis of macrophages

    PubMed Central

    Wang, Wenyan; Li, Ting; Wang, Xiaolin; Yuan, Wanxiong; Cheng, Yingying; Zhang, Heyu; Xu, Enquan; Zhang, Yingmei; Shi, Shuang; Ma, Dalong; Han, Wenling

    2015-01-01

    FAM19A4 is an abbreviation for family with sequence similarity 19 (chemokine (C–C motif)-like) member A4, which is a secretory protein expressed in low levels in normal tissues. The biological functions of FAM19A4 remain to be determined, and its potential receptor(s) is unclarified. In this study, we demonstrated that FAM19A4 was a classical secretory protein and we verified for the first time that its mature protein is composed of 95 amino acids. We found that the expression of this novel cytokine was upregulated in lipopolysaccharide (LPS)-stimulated monocytes and macrophages and was typically in polarized M1. FAM19A4 shows chemotactic activities on macrophages and enhances the macrophage phagocytosis of zymosan both in vitro and in vivo with noticeable increases of the phosphorylation of protein kinase B (Akt). FAM19A4 can also increase the release of reactive oxygen species (ROS) upon zymosan stimulation. Furthermore, based on receptor internalization, radio ligand binding assays and receptor blockage, we demonstrated for the first time that FAM19A4 is a novel ligand of formyl peptide receptor 1 (FPR1). The above data indicate that upon inflammatory stimulation, monocyte/macrophage-derived FAM19A4 may play a crucial role in the migration and activation of macrophages during pathogenic infections. PMID:25109685

  15. Chlorhexidine gel associated with papain in pulp tissue dissolution

    PubMed Central

    Couto De Oliveira, Gabriel; Ferraz, Caio Souza; Andrade Júnior, Carlos Vieira

    2013-01-01

    Objectives This study aimed to evaluate the capacity of 2% chlorhexidine gel associated with 8% papain gel in comparison with 5.25% sodium hypochlorite in bovine pulp tissue dissolution. Materials and Methods Ninety bovine pulps of standardized sizes were used and fragmented into 5-mm sizes. The fragments were removed from the root middle third region. They were divided into 6 experimental groups (n = 15), 1) 8% papain; 2) 2% chlorhexidine; 3) 2% chlorhexidine associated with 8% papain; 4) 0.9% saline solution; 5) 2.5% sodium hypochlorite; and 6) 5.25% sodium hypochlorite. The pulp fragments were weighed and put into immobile test tubes for dissolution for time intervals of 30, 60, 90, and 120 min. Results The 5.25% sodium hypochlorite had greater dissolution potential than the pure papain, and when associated with chlorhexidine, both promoted greater dissolution than did the saline solution and 2% chlorhexidine groups (p < 0.05). The 2.5% sodium hypochlorite promoted dissolution to a lesser extent than the groups with papain within a period of 30 min (p < 0.05), but, was comparable to the saline solution and chlorhexidine. After 120 min, the 2.5% and 5.25% sodium hypochlorite promoted dissolution of 100% of the pulp fragments, and papain, 61%, while chlorhexidine associated with papain and chlorhexidine alone dissolved only 55% and 3%, respectively. Conclusions The 8% papain in gel, both alone and in association with chlorhexidine, was able to dissolve bovine pulp tissue, but to a lesser extent than did 5.25% sodium hypochlorite. PMID:24303355

  16. Effect of bacteria and dissolved organics on mineral dissolution kinetics:

    NASA Astrophysics Data System (ADS)

    Pokrovsky, Oleg; Shirokova, Liudmila; Benezeth, Pascale; Zabelina, Svetlana

    2010-05-01

    Quantification of the effect of microorganisms and associated organic ligands on mineral dissolution rate is one among the last remaining challenges in modeling of water-rock interactions under earth surface and subsurface environments. This is especially true for deep underground settings within the context of CO2 capture, sequestration and storage. First, elevated CO2 pressures create numerous experimental difficulties for performing robust flow-through experiments at a given saturation state. Second, reactivity of main rock-forming minerals in abiotic systems at pCO2 >> 1 atm and circumneutral pH is still poorly constrained. And third, most of microbial habitats of the subsurface biosphere are not suitable for routine culturing in the laboratory, many of them are anaerobic and even strictly anaerobic, and many bacteria and archae cultures can live only in the consortium of microorganisms which is very hard to maintain at a controlled and stable biomass concentration. For experimental modeling of bio-mineral interactions in the laboratory, two other main conceptual challenges exist. Typical concentration of dissolved organic carbon that serves as a main nutrient for heterotrophic bacteria in underground waters rarely exceeds 3-5 mg/L. Typical concentration of DOC in nutrient media used for bacteria culturing is between 100 and 10,000 mg/L. Therefore, performing mineral-bacteria interactions in the laboratory under environmentally-sound conditions requires significant dilution of the nutrient media or the use of flow-through reactors. Concerning the effect of organic ligands and bacterial excudates on rock-forming mineral dissolution, at the present time, mostly empirical (phenomenological) approach can be used. Indeed, the pioneering studies of Stumm and co-workers have established a firm basis for modeling the catalyzing and inhibiting effects of ligands on metal oxide dissolution rate. This approach, very efficient for studying the interaction of organic and

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

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

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

  18. Dissolution test acceptance sampling plans.

    PubMed

    Tsong, Y; Hammerstrom, T; Lin, K; Ong, T E

    1995-07-01

    The U.S. Pharmacopeia (USP) general monograph provides a standard for dissolution compliance with the requirements as stated in the individual USP monograph for a tablet or capsule dosage form. The acceptance rules recommended by USP have important roles in the quality control process. The USP rules and their modifications are often used as an industrial lot release sampling plan, where a lot is accepted when the tablets or capsules sampled are accepted as proof of compliance with the requirement. In this paper, the operating characteristics of the USP acceptance rules are reviewed and compared to a selected modification. The operating characteristics curves show that the USP acceptance rules are sensitive to the true mean dissolution and do not reject a lot or batch that has a large percentage of tablets that dissolve with less than the dissolution specification.

  19. Mechanism of single-layer 193-nm dissolution inhibition resist

    NASA Astrophysics Data System (ADS)

    Yan, Zhenglin; Houlihan, Francis M.; Reichmanis, Elsa; Nalamasu, Omkaram; Reiser, Arnost; Dabbagh, Gary; Hutton, Richard S.; Osei, Dan; Sousa, Jose; Bolan, Kevin J.

    2000-06-01

    We have found that the progress of developer base into films of terpolymers of norbornene (NB)-maleic anhydride (MA) and acrylic acid (AA) is a percolation process with a critical site concentration of x(c) equals 0.084 which suggests that every acrylic acid site in the terpolymer of norbornene-maleic anhydride-acrylic acid can make 12 monomer units of the polymer water compatible. In practice these systems are being used with various tert-butyl esters of cholic acid as dissolution inhibitors. The cholates differ very much in their dissolution inhibition factors (lowest t-butyl cholate (1.3) to highest t-butyl lithocholate glutarate dimer (7.4). The change in these factors corrected for molarity follow the hydrophobic character of the dissolution as measured by log(p). A quick screening method has also been established to evaluate dissolution inhibitors based on our observation that the cloud point (the volume % acetone in a water/acetone which gives persistent cloudiness) parallels the dissolution inhibiting power as measured by the dissolution inhibition factor. For dissolution promotion, optimal results are obtained with t-butyl 1,3,5-cyclohexanetricarboxylate (f equals -6.3) and poorest results with t-butyl lithocholate (f equals -2.8); this appears to track with the number of carboxyl groups and the hydrophobicity of the carboxylic acids. The Rmax found for resist formulations tracks well with these findings. Another factor in determining the ultimate achievable contrast is the degree of acidolytic deprotection achieved by the material. It appears that acidolyticaly cleaveable carboxylate esters with a higher concentration of electron withdrawing groups such as t-butyl 1,3,5-cyclohexanetricarboxylate are more effective.

  20. Bioenhanced Dissolution of PCE from DNAPL Pools: Large Tank Experiments

    NASA Astrophysics Data System (ADS)

    Glover, K. C.; Illangasekare, T. H.; Munakata Marr, J.; Philippe, P.

    2006-12-01

    Long-term persistence of chlorinated DNAPL has driven interest in source-depletion technologies. Recent flow- cell experiments demonstrated that microbial reductive dehalogenation can significantly enhance dissolution of high saturation pools of DNAPL. Modeling of these experiments showed that bioenhanced mass transfer can be simulated by linking abiotic DNAPL dissolution with aqueous-phase biodegradation and solute transport. For many technologies, the scale of application affects DNAPL removal efficiency and downgradient mass flux. However, detailed characterization of processes at field scales rarely is possible. As described in this presentation, scale-dependency of bioenhanced mass transfer was characterized in detail by conducting dissolution experiments in large 2-D tanks packed with homogeneous or heterogeneous sand units. Biotic and abiotic dissolution experiments were conducted with DNAPL pools at a range of saturations. Key experimental results follow. (1) Mass flux from intermediate-scale sources was significantly enhanced by biological activity. Compared with results of flow-cell experiments at similar saturations and Darcy velocities, enhancement did not decline with increasing source volume. (2) Saturation transition zones at tops of pools were key zones of bioenhanced dissolution. Electron-donor advection within these zones promoted PCE degradation, lowering aqueous PCE concentrations, and enhancing dissolution gradients. (3) Biodegradation to DCE occurred in the vicinity of pools, followed by downgradient conversion to vinyl chloride and ethene. (4) Gas accumulation, associated with ethene and vinyl chloride production downstream and electron-donor consumption upstream of sources, was significant. (5) Though inoculation occurred solely within the source zone, dechlorinating microbes migrated rapidly into downgradient areas. After three months, microbe distribution was nearly uniform, regardless of porous media heterogeneity. These results suggest

  1. Bench Scale Saltcake Dissolution Test Report

    SciTech Connect

    BECHTOLD, D.B.; PACQUET, E.A.

    2000-12-06

    A potential scenario for retrieving saltcake from single shell tanks is the ''Rainbird{reg_sign} sprinkler'' method. Water is distributed evenly across the surface of the saltcake and allowed to percolate by gravity through the waste. The salt dissolves in the water, forming a saturated solution. The saturated liquid is removed by a saltwell pump situated near the bottom of the tank. By this method, there is never a large inventory of liquid in the tank that could pose a threat of leakage. There are many variables or factors that can influence the hydrodynamics of this retrieval process. They include saltcake porosity; saltwell pumping rate; salt dissolution chemistry; factors that could promote flow channeling (e.g. tank walls, dry wells, inclusions or discontinuities in the saltcake); method of water distribution; plug formation due to crystal formations or accumulation of insoluble solids. A brief literature search indicates that very little experimental data exist on these aspects of saltcake dissolution (Wiersma 1996, 1997). The tests reported here were planned (Herting, 2000) to provide preliminary data and information for planning future, scaled-up tests of the sprinkler method.

  2. The TLR9 ligand CpG promotes the acquisition of Plasmodium falciparum-specific memory B cells in malaria-naive individuals.

    PubMed

    Crompton, Peter D; Mircetic, Marko; Weiss, Greta; Baughman, Amy; Huang, Chiung-Yu; Topham, David J; Treanor, John J; Sanz, Iñaki; Lee, F Eun-Hyung; Durbin, Anna P; Miura, Kazutoyo; Narum, David L; Ellis, Ruth D; Malkin, Elissa; Mullen, Gregory E D; Miller, Louis H; Martin, Laura B; Pierce, Susan K

    2009-03-01

    Despite the central role of memory B cells (MBC) in protective immune responses, little is understood about how they are acquired in naive individuals in response to Ag exposure, and how this process is influenced by concurrent activation of the innate immune system's TLR. In this longitudinal study of malaria-naive individuals, we examined the MBC response to two candidate malaria vaccines administered with or without CpG, a TLR9 ligand. We show that the acquisition of MBC is a dynamic process in which the vaccine-specific MBC pool rapidly expands and then contracts, and that CpG enhances the kinetics, magnitude, and longevity of this response. We observed that the percentage of vaccine-specific MBC present at the time of reimmunization predicts vaccine-specific Ab levels 14 days later; and that at steady-state, there is a positive correlation between vaccine-specific MBC and Ab levels. An examination of the total circulating MBC and plasma cell pools also suggests that MBC differentiate into plasma cells through polyclonal activation, independent of Ag specificity. These results provide important insights into the human MBC response, which can inform the development of vaccines against malaria and other pathogens that disrupt immunological memory. PMID:19234231

  3. Sema4D, the ligand for Plexin B1, suppresses c-Met activation and migration and promotes melanocyte survival and growth.

    PubMed

    Soong, Joanne; Chen, Yulin; Shustef, Elina M; Scott, Glynis A

    2012-04-01

    Semaphorins are secreted and membrane-bound proteins involved in neural pathfinding, organogenesis, and tumor progression, through Plexin and neuropilin receptors. We recently reported that Plexin B1, the Semaphorin 4D (Sema4D) receptor, is a tumor-suppressor protein for melanoma, which functions, in part, through inhibition of the oncogenic c-Met tyrosine kinase receptor. In this report, we show that Sema4D is a protective paracrine factor for normal human melanocyte survival in response to UV irradiation, and that it stimulates proliferation and regulates the activity of the c-Met receptor. c-Met receptor signaling stimulates melanocyte migration, partly through downregulation of the cell adhesion molecule E-cadherin. Sema4D suppressed activation of c-Met in response to its ligand, hepatocyte growth factor (HGF), and partially blocked the suppressive effects of HGF on E-cadherin expression in melanocytes and HGF-dependent migration. These data demonstrate a role for Plexin B1 in maintenance of melanocyte survival and proliferation in the skin, and suggest that Sema4D and Plexin B1 act cooperatively with HGF and c-Met to regulate c-Met-dependent effects in human melanocytes. Because our data show that Plexin B1 is profoundly downregulated by UVB in melanocytes, loss of Plexin B1 may accentuate HGF-dependent effects on melanocytes, including melanocyte migration.

  4. Marital dissolution: an economic analysis.

    PubMed

    Hunter, K A

    1984-01-01

    A longitudinal analysis of factors affecting marital dissolution in the United States is presented using data from the Coleman-Rossi Retrospective Life History. Factors considered include labor force participation of both spouses, wage growth, size of family unit, age at marriage, and educational status. The study is based on the economic analysis approach developed by Gary S. Becker and others.

  5. Formulations for iron oxides dissolution

    DOEpatents

    Horwitz, Earl P.; Chiarizia, Renato

    1992-01-01

    A mixture of a di- or polyphosphonic acid and a reductant wherein each is present in a sufficient amount to provide a synergistic effect with respect to the dissolution of metal oxides and optionally containing corrosion inhibitors and pH adjusting agents.

  6. Stoichiometry of smectite dissolution reaction

    NASA Astrophysics Data System (ADS)

    Metz, Volker; Amram, Keren; Ganor, Jiwchar

    2005-04-01

    The dissolution stoichiometry of smectite-rich bentonites SAz-1, STx-1 and SWy-1 was studied at 50°C and pH 2 and 3 using flow-through reactors. In addition to smectite, these samples contain considerable amounts of silica phases (quartz, cristobalite and/or amorphous silica). As a result, the molar Al/Si ratios of the bulk samples are significantly lower than those of the pure smectite. Smectite dissolution was highly incongruent during the first few hundred to few thousand hours of the experiments. Release rates of Si, Mg, Ca and Na underwent a distinct transition from an initial period of rapid release to significantly lower release rate at steady state. A reversed trend was observed for release of Al, which gradually increased from very low starting release rate to higher release rate at steady state. At steady state the ratio of released Al to released Si was found to be constant and independent of the experimental conditions. We suggest that this ratio represents the Al/Si ratio of the smectite itself, and it is not influenced by the presence of accessory phases in the sample. The rapid release of calcium, sodium and magnesium from the interlayer sites is explained by ion-exchange reactions, whereas the fast release of silicon is explained by dissolution of amorphous silica. We interpret the initial slow release of Al as the result of inhibition of smectite dissolution due to coating or cementation of the smectite aggregates by amorphous silica. As the silica is dissolved, the aggregates fall apart and more smectite surfaces are exposed, resulting in an increase in the smectite dissolution rate. Thereafter, the system approaches steady state, in which the major tetrahedral and octahedral cations of smectite are released congruently.

  7. Bacterially enhanced dissolution of meta-autunite

    SciTech Connect

    Smeaton, C.M.; Weisener, C.G.; Burns, P.C.; Fryer, B.J.; Fowle, D.A.

    2008-12-15

    The release of U from the mineral meta-autunite {l_brace}Ca[(UO{sub 2})(PO{sub 2})](H{sub 2}O){sub 6}{r_brace} was evaluated using spectroscopy, aqueous geochemistry, and electron microscopy in a minimal media with the dissimilatory metal-reducing bacterium Shewanella putrefaciens 200R. The onset of anaerobic conditions resulted in the rapid release of U and phosphate to solution followed by the reprecipitation of meta-autinite. Spectroscopy measurements (XANES) indicated that the U was not released via reduction during the bacterial incubations, but instead dissolution was promoted by uptake and immobilization of P by the bacterial cells. Our results suggest that U(VI) in 'refractory' P mineral phases may be mobilized from U mill tailings and/or U disposal sites and that the nutrient status (P) of the geologic setting may be a predictor for the lability of U in these environments.

  8. The coordinated increased expression of biliverdin reductase and heme oxygenase-2 promotes cardiomyocyte survival: a reductase-based peptide counters β-adrenergic receptor ligand-mediated cardiac dysfunction

    PubMed Central

    Ding, Bo; Gibbs, Peter E. M.; Brookes, Paul S.; Maines, Mahin D.

    2011-01-01

    HO-2 oxidizes heme to CO and biliverdin; the latter is reduced to bilirubin by biliverdin reductase (BVR). In addition, HO-2 is a redox-sensitive K/Ca2-associated protein, and BVR is an S/T/Y kinase. The two enzymes are components of cellular defense mechanisms. This is the first reporting of regulation of HO-2 by BVR and that their coordinated increase in isolated myocytes and intact heart protects against cardiotoxicity of β-adrenergic receptor activation by isoproterenol (ISO). The induction of BVR mRNA, protein, and activity and HO-2 protein was maintained for ≥96 h; increase in HO-1 was modest and transient. In isolated cardiomyocytes, experiments with cycloheximide, proteasome inhibitor MG-132, and siBVR suggested BVR-mediated stabilization of HO-2. In both models, activation of BVR offered protection against the ligand's stimulation of apoptosis. Two human BVR-based peptides known to inhibit and activate the reductase, KKRILHC281 and KYCCSRK296, respectively, were tested in the intact heart. Perfusion of the heart with the inhibitory peptide blocked ISO-mediated BVR activation and augmented apoptosis; conversely, perfusion with the activating peptide inhibited apoptosis. At the functional level, peptide-mediated inhibition of BVR was accompanied by dysfunction of the left ventricle and decrease in HO-2 protein levels. Perfusion of the organ with the activating peptide preserved the left ventricular contractile function and was accompanied by increased levels of HO-2 protein. Finding that BVR and HO-2 levels, myocyte apoptosis, and contractile function of the heart can be modulated by small human BVR-based peptides offers a promising therapeutic approach for treatment of cardiac dysfunctions.—Ding, B., Gibbs, P. E. M., Brookes, P. S., Maines, M. D. The coordinated increased expression of biliverdin reductase and heme oxygenase-2 promotes cardiomyocyte survival; a reductase-based peptide counters β-adrenergic receptor ligand-mediated cardiac dysfunction

  9. A Role for Antibiotics in Mineral Dissolution and Biofilm Physiology

    NASA Astrophysics Data System (ADS)

    Newman, D. K.

    2002-12-01

    Respiration by bacteria is remarkable due to their ability to use a variety of compounds, including insoluble minerals, as terminal electron acceptors. How bacteria solve the problem of breathing something that is solid is poorly understood, but recent evidence points to the role of redox active natural products in shuttling electrons between microbes and minerals. Given the ubiquity of these substances in natural waters and soils, we must now revisit previous conclusions about whether direct contact between microbes and minerals is necessary to promote reductive mineral dissolution. To explore the degree to which extracellular electron transfer catalyzes important biogeochemical processes, we are studying the types of molecules that function as electron shuttles, including redox active antibiotics. I will discuss my laboratory's current understanding of how interspecies exchange of these molecules promotes mineral dissolution, as well as our emerging hypotheses regarding their function in biofilms.

  10. Dissolution patterns on caramel blocks

    NASA Astrophysics Data System (ADS)

    Cohen, Caroline; Derr, Julien; Berhanu, Michael; Courrech Du Pont, Sylvain

    2015-11-01

    We investigate erosion by dissolution processes. We perform laboratory experiments on hard caramel bodies, which dissolve on a short timescale, compared to geological material such as limestone. We put a block of caramel, tilted from the horizontal, in a water tank without flow. The dissolution syrup, which is denser than pure water, sinks and the flow detaching from the surface creates patterns underneath the caramel block. These patterns result from the coupled dynamics of the flow detaching and the eroding surface and are reminiscent of scallops observed in the walls of phreatic cave passages. We investigate the mechanisms of formation of these structures and their evolution depending on several parameters such as the fluid density or the flow velocity. We finally parallel the formation of patterns on melting iceberg.

  11. Marital Dissolution Among Interracial Couples.

    PubMed

    Zhang, Yuanting; Van Hook, Jennifer

    2009-02-01

    Increases in interracial marriage have been interpreted as reflecting reduced social distance among racial and ethnic groups, but little is known about the stability of interracial marriages. Using six panels of Survey of Income and Program Participation (N = 23,139 married couples), we found that interracial marriages are less stable than endogamous marriages, but these findings did not hold up consistently. After controlling for couple characteristics, the risk of divorce or separation among interracial couples was similar to the more-divorce-prone origin group. Although marital dissolution was found to be strongly associated with race/ethnicity, the results failed to provide evidence that interracial marriage is associated with an elevated risk of marital dissolution.

  12. Mass exchange during simultaneous grinding and dissolution

    SciTech Connect

    Aksel'rud, G.A.; Semenishin, E.M.; Kopyt, S.Ya.; Trotskii, V.I.

    1988-03-20

    Extraction of ore components of interest has a number of disadvantages, one of which being low efficiency. Combining the grinding and dissolution steps in one apparatus makes the process more efficient. Adoption of this technology, however, requires theoretical and mathematical studies. This paper reports the kinetics of simultaneous grinding and dissolution of copper-containing minerals. Simultaneous grinding and dissolution accelerated several fold the mass transfer of components of interest in the interaction of malachite and azurite with sulfuric acid solutions. The complete dissolution time was determined by adding the experimental rates of dissolution and abrasion.

  13. Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

    SciTech Connect

    Ravichandran, M.; Ryan, J.N.; Aiken, G.R.; Reddy, M.M.

    1998-11-01

    Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca{sup 2+}. Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in Dl water had no detectable dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates correlated positively with enhanced cinnabar dissolution. {zeta}-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

  14. Calcination/dissolution residue treatment

    SciTech Connect

    Knight, R.C.; Creed, R.F.; Patello, G.K.; Hollenberg, G.W.; Buehler, M.F.; O`Rourke, S.M.; Visnapuu, A.; McLaughlin, D.F.

    1994-09-01

    Currently, high-level wastes are stored underground in steel-lined tanks at the Hanford site. Current plans call for the chemical pretreatment of these wastes before their immobilization in stable glass waste forms. One candidate pretreatment approach, calcination/dissolution, performs an alkaline fusion of the waste and creates a high-level/low-level partition based on the aqueous solubilities of the components of the product calcine. Literature and laboratory studies were conducted with the goal of finding a residue treatment technology that would decrease the quantity of high-level waste glass required following calcination/dissolution waste processing. Four elements, Fe, Ni, Bi, and U, postulated to be present in the high-level residue fraction were identified as being key to the quantity of high-level glass formed. Laboratory tests of the candidate technologies with simulant high-level residues showed reductive roasting followed by carbonyl volatilization to be successful in removing Fe, Ni, and Bi. Subsequent bench-scale tests on residues from calcination/dissolution processing of genuine Hanford Site tank waste showed Fe was separated with radioelement decontamination factors of 70 to 1,000 times with respect to total alpha activity. Thermodynamic analyses of the calcination of five typical Hanford Site tank waste compositions also were performed. The analyses showed sodium hydroxide to be the sole molten component in the waste calcine and emphasized the requirement for waste blending if fluid calcines are to be achieved. Other calcine phases identified in the thermodynamic analysis indicate the significant thermal reconstitution accomplished in calcination.

  15. Optimizing dissolution dynamic nuclear polarization

    NASA Astrophysics Data System (ADS)

    Bornet, Aurélien; Jannin, Sami

    2016-03-01

    This article is a short review of some of our recent developments in dissolution dynamic nuclear polarization (d-DNP). We present the basic principles of d-DNP, and motivate our choice to step away from conventional approaches. We then introduce a modified d-DNP recipe that can be summed up as follows: Using broad line polarizing agents to efficiently polarize 1H spins. Increasing the magnetic field to 6.7 T and above. Applying microwave frequency modulation. Applying 1H-13C cross polarization. Transferring hyperpolarized solution through a magnetic tunnel.

  16. DISSOLUTION OF NEPTUNIUM OXIDE RESIDUES

    SciTech Connect

    Kyser, E

    2009-01-12

    This report describes the development of a dissolution flowsheet for neptunium (Np) oxide (NpO{sub 2}) residues (i.e., various NpO{sub 2} sources, HB-Line glovebox sweepings, and Savannah River National Laboratory (SRNL) thermogravimetric analysis samples). Samples of each type of materials proposed for processing were dissolved in a closed laboratory apparatus and the rate and total quantity of off-gas were measured. Samples of the off-gas were also analyzed. The quantity and type of solids remaining (when visible) were determined after post-dissolution filtration of the solution. Recommended conditions for dissolution of the NpO{sub 2} residues are: Solution Matrix and Loading: {approx}50 g Np/L (750 g Np in 15 L of dissolver solution), using 8 M nitric acid (HNO{sub 3}), 0.025 M potassium fluoride (KF) at greater than 100 C for at least 3 hours. Off-gas: Analysis of the off-gas indicated nitric oxide (NO), nitrogen dioxide (NO{sub 2}) and nitrous oxide (N{sub 2}O) as the only identified components. No hydrogen (H{sub 2}) was detected. The molar ratio of off-gas produced per mole of Np dissolved ranged from 0.25 to 0.4 moles of gas per mole of Np dissolved. A peak off-gas rate of {approx}0.1 scfm/kg bulk oxide was observed. Residual Solids: Pure NpO{sub 2} dissolved with little or no residue with the proposed flowsheet but the NpCo and both sweepings samples left visible solid residue after dissolution. For the NpCo and Part II Sweepings samples the residue amounted to {approx}1% of the initial material, but for the Part I Sweepings sample, the residue amounted to {approx}8 % of the initial material. These residues contained primarily aluminum (Al) and silicon (Si) compounds that did not completely dissolve under the flowsheet conditions. The residues from both sweepings samples contained minor amounts of plutonium (Pu) particles. Overall, the undissolved Np and Pu particles in the residues were a very small fraction of the total solids.

  17. Fractal patterns from chemical dissolution

    NASA Astrophysics Data System (ADS)

    Daccord, Gérard; Lenormand, Roland

    1987-01-01

    The highly ramified patterns1,2 produced by the flow of a reactive fluid through a soluble porous medium have never been quantitatively described. The theoretical understanding of this phenomenon is limited to very simple conditions (such as the flow of a liquid through a; capillary3) due to the complexity of the coupling between the chemical reaction and the fluid flow. We show here that the dissolution patterns (DP) obtained experimentally by injecting water through pure plaster are fractal, for different geometries of the samples. In two dimensions, these DP are remarkably'similar to patterns associated with diffusion-limited aggregation4-6 (DLA), that is, dielectric breakdown7, viscous fingering8,9 and diffusion-limited polymerization10. In three dimensions, we compare them with DLA clusters grown in the same boundary conditions and find a good qualitative and quantitative similarity. These results should be of interest in different areas where chemical dissolution of porous media by a flowing fluid occurs, for example, in nature (the formation of caves) and in industry (in the oil industry where acids are routinely injected into oil reservoirs).

  18. DISSOLUTION OF LANTHANUM FLUORIDE PRECIPITATES

    DOEpatents

    Fries, B.A.

    1959-11-10

    A plutonium separatory ore concentration procedure involving the use of a fluoride type of carrier is presented. An improvement is given in the derivation step in the process for plutonium recovery by carrier precipitation of plutonium values from solution with a lanthanum fluoride carrier precipitate and subsequent derivation from the resulting plutonium bearing carrier precipitate of an aqueous acidic plutonium-containing solution. The carrier precipitate is contacted with a concentrated aqueous solution of potassium carbonate to effect dissolution therein of at least a part of the precipitate, including the plutonium values. Any remaining precipitate is separated from the resulting solution and dissolves in an aqueous solution containing at least 20% by weight of potassium carbonate. The reacting solutions are combined, and an alkali metal hydroxide added to a concentration of at least 2N to precipitate lanthanum hydroxide concomitantly carrying plutonium values.

  19. Effects of Natural Organic Matter Properties on the Dissolution Kinetics of Zinc Oxide Nanoparticles.

    PubMed

    Jiang, Chuanjia; Aiken, George R; Hsu-Kim, Heileen

    2015-10-01

    The dissolution of zinc oxide (ZnO) nanoparticles (NPs) is a key step of controlling their environmental fate, bioavailability, and toxicity. Rates of dissolution often depend upon factors such as interactions of NPs with natural organic matter (NOM). We examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution using anodic stripping voltammetry to directly measure dissolved zinc concentrations. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg C L(-1)) for Suwannee River humic and fulvic acids and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. The findings of this study facilitate a better understanding of the fate of ZnO NPs in organic-rich aquatic environments and highlight SUVA as a facile and useful indicator of NOM interactions with metal-based nanoparticles.

  20. Pervasive burial dissolution of early and late dolomites in Devonian pools, Alberta, western Canada

    SciTech Connect

    Dravis, J.J. ); Muir, I.D. )

    1991-03-01

    Middle Devonian Keg River and Muskeg pools along the northern margin of Rainbow basin in northern Alberta produce mainly from secondary porosity created by dissolution of replacement dolomites and cements, including saddle dolomites. Resultant pores are predominantly vug and moldic and often microporous. Coarse vuggy porosity is also associated with Zebra dolomites. Several relationships confirm the burial dissolution of dolomites in these sequences. First, dolomites which replaced stylolitic sediment, including saddle dolomites, are leached, as shown by fluorescence microscopy. Second, high amounts of secondary porosity are preserved in highly stylolitic dolomites, often directly adjacent to pressure solution seams. Third, pressure solution seams terminate directly into secondary porosity. And fourth, fractures which cut stylolites also commonly feed directly into secondary pores. These petrographic relationships are consistent only if dolomite dissolution and secondary porosity development were contemporaneous with or postdated pressure solution. The spatial juxtaposition of fractures and stylolites with secondary porosity implies these diagenetic fabrics served as pathways for burial fluids promoting dolomite dissolution. Given the regional extent of pervasive dolomite dissolution, dolomite stability in these sequences is not a function of the type or relative age of dolomite crystals precipitated. Rather, pore-fluid chemistry appears to be the major control. Calcium-rich burial fluids, responsible for emplacement of burial anhydrites and fluorite cements, are thought to promote the deep-burial dolomite dissolution and secondary porosity development in these pools.

  1. Mechanism of Non-Steady State Dissolution of Goethite in the Presence of Siderophores

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

    Iron is an essential micronutrient for almost all known organisms. Bacteria, fungi, and graminaceous plants are capable of exuding siderophores as part of an iron acquisition strategy. The production of these strong iron chelating ligands is induced by iron limited conditions. Grasses under iron stress, for example, exude phytosiderophores into the rhizosphere in a special diurnal rhythm (Roemheld and Marschner 1986). A few hours after sunrise the exudation starts, culminates around noon and is shut down again until about 4 hours after noon. The phytosiderophores diffuse into the rhizosphere (Marschner et al. 1986) and are passively back transported to the plants by advective flow induced by high transpiration around noon. Despite a fairly short residence time of the phytosiderophores in the rhizosphere, it is a very effective strategy for iron acquisition. To investigate the effect of such pulse inputs of siderophores on iron acquisition, we studied the dissolution mechanism of goethite (alpha-FeOOH), a mineral phase common in soils, under non-steady state conditions. In consideration of the chemical complexity of the rhizosphere, we also investigated the effect of other organic ligands commonly found in the rhizosphere (e. g. oxalate) on the dissolution kinetics. The dissolution experiments were conducted in batch reactors with a constant goethite solids concentration of 2.5 g/l, an ionic strength of 0.01 M, a pH of 6 and 100 microM oxalate. To induce non-steady state conditions, 3 mM phytosiderophores were added to a batch after the goethite-oxalate suspension reacted for a certain time period. Before the siderophore was added to the goethite-oxalate suspension, no dissolution of iron was observed. But, with the addition of the siderophore, a high rate was observed for the iron mobilization under these non-steady state conditions that subsequently was followed by a slow steady state dissolution rate. The results of these non-steady state experiments are very

  2. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  3. CALCIUM CARBONATE DISSOLUTION RATE IN LIMESTONE CONTACTORS

    EPA Science Inventory

    The rate of carbonate mineral dissolution from limestone was studied using a rotating disk apparatus and samples of limestone of varied composition. The purpose of this study was to determine the effect of limestone composition on the kinetics of carbonate mineral dissolution. Th...

  4. Stirring effect on kaolinite dissolution rate

    NASA Astrophysics Data System (ADS)

    Metz, Volker; Ganor, Jiwchar

    2001-10-01

    Experiments were carried out measuring kaolinite dissolution rates using stirred and nonstirred flow-through reactors at pHs 2 to 4 and temperatures of 25°C, 50°C, and 70°C. The results show an increase of kaolinite dissolution rate with increasing stirring speed. The stirring effect is reversible, i.e., as the stirring slows down the dissolution rate decreases. The effect of stirring speed on kaolinite dissolution rate is higher at 25°C than at 50°C and 70°C and at pH 4 than at pHs 2 and 3. It is suggested that fine kaolinite particles are formed as a result of stirring-induced spalling or abrasion of kaolinite. These very fine particles have an increased ratio of reactive surface area to specific surface area, which results in enhancement of kaolinite dissolution rate. A balance between production and dissolution of the fine particles explains both the reversibility and the temperature and pH dependence of the stirring effect. Since the stirring effect on kaolinite dissolution rate varies with temperature and pH, measurement of kinetic parameters such as activation energy may be influenced by stirring. Therefore, standard use of nonagitated reaction vessels for kinetic experiments of mineral dissolution and precipitation is recommended, at least for slow reactions that are surface controlled.

  5. Nanosizing of drugs: Effect on dissolution rate

    PubMed Central

    Dizaj, S. Maleki; Vazifehasl, Zh.; Salatin, S.; Adibkia, Kh.; Javadzadeh, Y.

    2015-01-01

    The solubility, bioavailability and dissolution rate of drugs are important parameters for achieving in vivo efficiency. The bioavailability of orally administered drugs depends on their ability to be absorbed via gastrointestinal tract. For drugs belonging to Class II of pharmaceutical classification, the absorption process is limited by drug dissolution rate in gastrointestinal media. Therefore, enhancement of the dissolution rate of these drugs will present improved bioavailability. So far several techniques such as physical and chemical modifications, changing in crystal habits, solid dispersion, complexation, solubilization and liquisolid method have been used to enhance the dissolution rate of poorly water soluble drugs. It seems that improvement of the solubility properties ofpoorly water soluble drugscan translate to an increase in their bioavailability. Nowadays nanotechnology offers various approaches in the area of dissolution enhancement of low aqueous soluble drugs. Nanosizing of drugs in the form of nanoparticles, nanocrystals or nanosuspensions not requiring expensive facilities and equipment or complicated processes may be applied as simple methods to increase the dissolution rate of poorly water soluble drugs. In this article, we attempted to review the effects of nanosizing on improving the dissolution rate of poorly aqueous soluble drugs. According to the reviewed literature, by reduction of drug particle size into nanometer size the total effective surface area is increased and thereby dissolution rate would be enhanced. Additionally, reduction of particle size leads to reduction of the diffusion layer thickness surrounding the drug particles resulting in the increment of the concentration gradient. Each of these process leads to improved bioavailability. PMID:26487886

  6. Thermal dissolution of solid fossil fuels

    SciTech Connect

    E.G. Gorlov

    2007-10-15

    The use of oil shales and coals in the processes of thermal dissolution is considered. It is shown that thermal dissolution is a mode of liquefaction of solid fossil fuels and can be used both independently and in combination with liquefaction of coals and processing of heavy petroleum residues.

  7. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  8. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  9. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  10. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  11. Dissolution enthalpies of cellulose in ionic liquids.

    PubMed

    Parviainen, Helena; Parviainen, Arno; Virtanen, Tommi; Kilpeläinen, Ilkka; Ahvenainen, Patrik; Serimaa, Ritva; Grönqvist, Stina; Maloney, Thaddeus; Maunu, Sirkka Liisa

    2014-11-26

    In this work, interactions between cellulose and ionic liquids were studied calorimetrically and by optical microscopy. Two novel ionic liquids (1,5-Diazabicyclo[4.3.0]non-5-enium propionate and N-methyl-1,5-diazabicyclo[4.3.0]non-5-enium dimethyl phosphate) and 1-ethyl-3-methylimidazolium acetate-water mixtures were used as solvents. Optical microscopy served in finding the extent of dissolution and identifying the dissolution pattern of the cellulose sample. Calorimetric studies identified a peak relating to dissolution of cellulose in solvent. The transition did, however, not indicate complete dissolution, but rather dissolution inside fibre or fibrils. This method was used to study differences between four cellulose samples with different pretreatment or origins.

  12. Dissolution enthalpies of cellulose in ionic liquids.

    PubMed

    Parviainen, Helena; Parviainen, Arno; Virtanen, Tommi; Kilpeläinen, Ilkka; Ahvenainen, Patrik; Serimaa, Ritva; Grönqvist, Stina; Maloney, Thaddeus; Maunu, Sirkka Liisa

    2014-11-26

    In this work, interactions between cellulose and ionic liquids were studied calorimetrically and by optical microscopy. Two novel ionic liquids (1,5-Diazabicyclo[4.3.0]non-5-enium propionate and N-methyl-1,5-diazabicyclo[4.3.0]non-5-enium dimethyl phosphate) and 1-ethyl-3-methylimidazolium acetate-water mixtures were used as solvents. Optical microscopy served in finding the extent of dissolution and identifying the dissolution pattern of the cellulose sample. Calorimetric studies identified a peak relating to dissolution of cellulose in solvent. The transition did, however, not indicate complete dissolution, but rather dissolution inside fibre or fibrils. This method was used to study differences between four cellulose samples with different pretreatment or origins. PMID:25256460

  13. Surface properties, solubility and dissolution kinetics of bamboo phytoliths

    NASA Astrophysics Data System (ADS)

    Fraysse, Fabrice; Pokrovsky, Oleg S.; Schott, Jacques; Meunier, Jean-Dominique

    2006-04-01

    Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of "soil" phytoliths ( pKsp0=2.74 at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction (ΔHr25-80°C=10.85kJ/mol) is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for "soil" (native) and "heated" (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-p K surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ⩽ pH ⩽ 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation: R=k1·{>SiOH2+}n+k2·{>SiOH0}+k3·{>SiO-}m, where {> i} stands for the concentration of the surface species present at the SiO 2-H 2O interface, ki are the rate constants of the three parallel reactions and n and m represent the order of the proton- and hydroxy-promoted reactions, respectively. It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ˜ 3. This can explain their good preservation in the acidic soil horizons of Réunion Island. In terms of silicon biogeochemical cycle, phytoliths represent a large buffering reservoir

  14. Chemical dissolution of sulfide minerals

    USGS Publications Warehouse

    Chao, T.T.; Sanzolone, R.F.

    1977-01-01

    Chemical dissolution treatments involving the use of aqua regia, 4 N HNO3, H2O2-ascorbic acid, oxalic acid, KClO3+HCl, and KClO3+HCl followed by 4 N HNO3 were applied to specimens of nine common sulfide minerals (galena, chalcopyrite, cinnabar, molybdenite, orpiment, pyrite, stibnite, sphalerite, and tetrahedrite) mixed individually with a clay loam soil. The resultant decrease in the total sulfur content of the mixture, as determined by using the Leco induction furnace, was used to evaluate the effectiveness of each chemical treatment. A combination of KClO3+HCl followed by 4 N HNO3 boiling gently for 20 min has been shown to be very effective in dissolving all the sulfide minerals. This treatment is recommended to dissolve metals residing in sulfide minerals admixed with secondary weathering products, as one step in a fractionation scheme whereby metals in soluble and adsorbed forms, and those associated with organic materials and secondary oxides, are first removed by other chemical extractants.

  15. Microbial extracellular polysaccharides and plagioclase dissolution

    NASA Astrophysics Data System (ADS)

    Welch, S. A.; Barker, W. W.; Banfield, J. F.

    1999-05-01

    Bytownite feldspar was dissolved in batch reactors in solutions of starch (glucose polymer), gum xanthan (glucose, mannose, glucuronic acid), pectin (poly-galacturonic acid), and four alginates (mannuronic and guluronic acid) with a range of molecular weights (low, medium, high and uncharacterized) to evaluate the effect of extracellular microbial polymers on mineral dissolution rates. Solutions were analyzed for dissolved Si and Al as an indicator of feldspar dissolution. At neutral pH, feldspar dissolution was inhibited by five of the acid polysaccharides, gum xanthan, pectin, alginate low, alginate medium, alginate high, compared to an organic-free control. An uncharacterized alginate substantially enhanced both Si and Al release from the feldspar. Starch, a neutral polysaccharide, had no apparent effect. Under mildly acidic conditions, initial pH ≈ 4, all of the polymers enhanced feldspar dissolution compared to the inorganic controls. Si release from feldspar in starch solution exceeded the control by a factor of three. Pectin and gum xanthan increased feldspar dissolution by a factor of 10, and the alginates enhanced feldspar dissolution by a factor of 50 to 100. Si and Al concentrations increased with time, even though solutions were supersaturated with respect to several possible secondary phases. Under acidic conditions, initial pH ≈ 3, below the pK a of the carboxylic acid groups, dissolution rates increased, but the relative increase due to the polysaccharides is lower, approximately a factor of two to ten. Microbial extracellular polymers play a complex role in mineral weathering. Polymers appear to inhibit dissolution under some conditions, possibly by irreversibly binding to the mineral surfaces. The extracellular polysaccharides can also enhance dissolution by providing protons and complexing with ions in solution.

  16. In silico dissolution rates of pharmaceutical ingredients

    NASA Astrophysics Data System (ADS)

    Dogan, Berna; Schneider, Julian; Reuter, Karsten

    2016-10-01

    The correlation between in vitro dissolution rates and the efficiency of drug formulations establishes an opportunity for accelerated drug development. Using in silico methods to predict the dissolution rates bears the prospect of further efficiency gains by avoiding the actual synthesis of candidate formulations. Here, we present a computational protocol that achieves such prediction for molecular crystals at low undersaturation. The protocol exploits the classic spiral dissolution model to minimize the number of material parameters that require explicit molecular simulations. Comparison to available data for acetylsalicylic acid and alpha lactose monohydrate indicates a tunable accuracy within one order of magnitude.

  17. A General Ligand Design for Gold Catalysis allowing Ligand-Directed Anti Nucleophilic Attack of Alkynes

    PubMed Central

    Wang, Yanzhao; Wang, Zhixun; Li, Yuxue; Wu, Gongde; Cao, Zheng; Zhang, Liming

    2014-01-01

    Most homogenous gold catalyses demand ≥0.5 mol % catalyst loading. Due to the high cost of gold, these reactions are unlikely to be applicable in medium or large scale applications. Here we disclose a novel ligand design based on the privileged biphenyl-2-phosphine framework that offers a potentially general approach to dramatically lowering catalyst loading. In this design, an amide group at the 3’ position of the ligand framework directs and promotes nucleophilic attack at the ligand gold complex-activated alkyne, which is unprecedented in homogeneous gold catalysis considering the spatial challenge of using ligand to reach antiapproaching nucleophile in a linear P-Au-alkyne centroid structure. With such a ligand, the gold(I) complex becomes highly efficient in catalyzing acid addition to alkynes, with a turnover number up to 99,000. Density functional theory calculations support the role of the amide moiety in directing the attack of carboxylic acid via hydrogen bonding. PMID:24704803

  18. FY 1999 Saltcake Dissolution Workshop

    SciTech Connect

    Beahm, E.C.

    2001-02-12

    During the FY 1998 Saltcake Dissolution Workshop, participants identified nine tasks to be performed prior to the FY 1999 workshop. Discussions during the workshop indicated that significant progress was made in each area. The workshop focused on the strengths and weaknesses of the Environmental Simulation Program (ESP). In addition, the ESP predictions for the Tank SY-101 remediation and the ESP validation efforts were evaluated. Finally, the need for a broader user base was identified. At the request of the Tank Waste Remediation System (TWRS), the ESP model was successfully utilized to predict the effects of Hanford tank farm operations such as waste transfers and water dilutions. The ESP model was originally developed to predict the compositions of solutions from off gas scrubbers. Therefore, the original database for the ESP model was designed for use with solutions with low ionic strengths. However, the Hanford tanks contain waste with very high ionic strengths. TWRS and Tank Focus Area (TFA) staff members have measured the solubilities of key components at high ionic strengths. The results from these studies were used to develop the Hanford database for the ESP model so the model could more accurately predict the compositions of Hanford waste streams with high ionic streams. The OLI Corporation, which developed the ESP model, has now incorporated most of the Hanford database into its standard ESP database. Another deficiency of the ESP model involves the lack of detailed documentation. Most new users of the ESP model normally encounter several obstacles. Therefore, TWRS management has proposed the development of an ESP user guide based on the experiences of TWRS and TFA researchers. The objective of the user guide is to make the ESP model more user friendly for the Hanford process engineers. The saltcake dissolution experiments at Hanford and the SOLGAS calculations at Oak Ridge are critically in the validation of the ESP model. Due to the high costs

  19. Predicting dissolution via hydrodynamics: salicylic acid tablets in flow through cell dissolution.

    PubMed

    Cammarn, S R; Sakr, A

    2000-05-25

    A model was established for the dissolution of non-disintegrating salicylic acid tablets as a function of hydrodynamic conditions in the Flow Through Cell system (USP Apparatus 4). The approach was to model the dissolution rate of the material as a function of the Reynold's number, the dimensionless engineering term that describes the degree of turbulence. The dissolution rate of USP calibrator salicylic acid tablets was measured as a function of tablet size, orientation within the cell, dissolution media flow rate, and cell size. All of these variables were found to have an effect on dissolution rate, consistent with theory. An equation to predict this dissolution was established as: N(SH)=-21.1+12.6xN(RE)(0.5), R(2)=0.99; 10

  20. [Phytobezoar dissolution with Coca-Cola].

    PubMed

    Martínez de Juan, F; Martínez-Lapiedra, C; Picazo, V

    2006-05-01

    The treatment of phytobezoar is empiric. The various therapeutic choices include dietary modifications, prokinetic drugs, gastric lavage, enzymatic dissolution, endoscopic treatment, and surgery. We present two cases of phytobezoar with successful outcome after Coca-Cola administration.

  1. Dissolution and Separation of Aluminum and Aluminosilicates

    SciTech Connect

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; Felker, Leslie Kevin; Mattus, Catherine H.

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.

  2. Dissolution and Separation of Aluminum and Aluminosilicates

    DOE PAGESBeta

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; Felker, Leslie Kevin; Mattus, Catherine H.

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as amore » function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

  3. [Dissolution study of the gentin tablets].

    PubMed

    Tsagareishvili, N T; Bakuridze, A D; Kurdiani, N G; Murtazashvili, T Zh

    2006-04-01

    To establish individual dissolution test for the tablets gentin, which have a marked influence on the secretory function of the stomach (increase the free acidity of the gastric juice and stimulate enzymoproduction function of the stomach), and gastroprotective functioning, the conditions for the test realization were studied and specified, using apparatus "Rotating Basket" (Dissolution test, apparatus 1, p.1791, USP XXIII, 1995). For the quantification of the active ingredients in buffer solutions chromatospectrophotometric method was used. The same conditions were used for the accomplishment of the dissolution test using apparatus "Rotating Paddle" (Dissolution test, apparatus 2, p.1791, USP XXIII, 1995). Metrologic characteristics were compared for the evaluation of the reproducibility of the results. Obtained data showed better reproducibility of the results for the apparatus "Rotating Paddle" compare to the apparatus "Rotating Basket". Estimated conditions are useful for the routine control of the tablets "Gentin" in the case of manufacturing.

  4. Nylon Dissolution in Nitric Acid Solutions

    SciTech Connect

    KESSINGER, GLENF.

    2004-06-16

    H Area Operations is planning to process Pu-contaminated uranium scrap in support of de-inventory efforts. Nylon bags will be used to hold materials to be dissolved in H-Canyon. Based on this set of twelve nylon dissolutions, it is concluded that (when other variables are held constant): increased acid concentration results in increased dissolution rates; increased acid concentration results in a lower dissolution onset temperature; little, if any, H plus is consumed during the depolymerization process; and 2.0-3.0 M HNO3, with 0.025 M KF and 2 g/L B, is satisfactory for the dissolution of nylon bag materials to be used during H-Canyon processing.

  5. A Social Psychological Perspective on Marital Dissolution

    ERIC Educational Resources Information Center

    Levinger, George

    1976-01-01

    The hypothetical constructs of attraction and barrier forces, as well as contrasting alternative attractions are used to organize the research literature on the determinants of marital stability and dissolution. (Author/AM)

  6. Differential dissolution susceptibility of Paleocene foraminiferal assemblage from Farafra Oasis, Egypt

    NASA Astrophysics Data System (ADS)

    Orabi, Orabi H.; Zaky, Amr S.

    2016-01-01

    Four inferred carbonate dissolution intervals are recognized at North Gunna section within the Dakhla and Esna formations (Paleocene) of the Farafra Oasis of Egypt as the following: 1) at the Danian/Selandian boundary (P3a/P3b), 2) at the upper part of Acarinina soldadoensis/Globanomalina pseudomenardii Subzone (P4c), 3) at the upper two third of the Morozvella velascoenis P5 Biozone and 4) at the Paleocene/Eocene boundary of Morozovella velascoensis/Morozovella aragonensis-Morozovelia subbotinae (P5/E5), where the P/E boundary is marked by major hiatus. The essential indicators of dissolution within the four intervals samples are low P/B ratios, high relative abundance of the agglutinated taxa, high relative abundance of calcareous taxa resistant to dissolution, especially Lenticulin, Cibicidoides and Anomalinoides and low relative abundance of susceptible calcareous taxa, such as unilocular, uniserial and biserial taxa for the benthics and non-muricate taxa for the planktonic, associated with the high percentage of organic carbon. The probably factors may contribute to the dissolution of planktonic foraminiferal tests in the four intervals of dissolution at the Farafra Oasis is that acidity produced by the degradation of organic matter promotes dissolution in sediment pore waters.

  7. Dissolution rates of prehnite, epidote, and albite

    SciTech Connect

    Rosemary, N.M. )

    1991-11-01

    Dissolution rates of prehnite and epidote in aqueous solutions were measured in the temperature range 25 to 90C, and as a function of pH. The dissolution rate of albite was measured at pH 1.4 at temperatures between 25 and 90C. Batch experiments using low ionic strength pH buffers in constant temperature water batch or ovens provided data on cumulative element release as a function of time. Steady state Si, Ca, Na, and Al release data obtained from these experiments were used to obtain limiting dissolution rates, where the term limiting rate denotes dissolution of a bulk mineral under conditions where it is far from equilibrium with the fluid. At 90C and at pH 1.4 to 6, prehnite and epidote dissolution rates decrease and are proportional to approximately {minus}0.3 pH for prehnite and {minus}0.2 pH for epidote. Above pH 6, prehnite dissolution becomes pH independent, by epidote dissolution increases with rates that are proportional to between +0.3 and +0.6 pH. Prehnite and epidote dissolution is linear and stoichiometric at low pH. At pH greater than 7, both minerals initially display preferential release of Si and Al relative to Ca; however, with increasing reaction dissolution becomes stoichiometric. This suggests that a Ca-enriched layer forms but reaches a steady state thickness which does not impede subsequent linear stoichiometric release. At pH 1.4, the limiting dissolution rate for albite is linear and stoichiometric. At pH 1.4, the activation energies are 18.12 {plus minus} 0.81 kcal mol{sup {minus}1} for prehnite, 19.76 {plus minus} 1.2 kcal mol{sup {minus}1} for epidote and 17.07 {plus minus} 1.6 kcal mol{sup {minus}1} for albite. At pH 6.5, the activation energy for prehnite dissolution is 20.73 {plus minus} 3.2 kcal mol{sup {minus}1}.

  8. Impact of iron chelators on short-term dissolution of basaltic glass

    NASA Astrophysics Data System (ADS)

    Perez, Anne; Rossano, Stéphanie; Trcera, Nicolas; Verney-Carron, Aurélie; Huguenot, David; van Hullebusch, Eric D.; Catillon, Gilles; Razafitianamaharavo, Angelina; Guyot, François

    2015-08-01

    Although microorganisms seem to play an important role in the alteration processes of basaltic glasses in solution, the elementary mechanisms involved remain unclear in particular with regard to the role of organic ligands excreted by the cells. Two glasses, one with Fe and one without Fe were synthesized to model basaltic glass compositions. Fe in the glass was mostly Fe(III) for enhancing interaction with siderophores, yet with small but significant amounts of Fe(II) (between 10% and 30% of iron). The prepared samples were submitted to abiotic alteration experiments in buffered (pH 6.4) diluted solutions of metal-specific ligands, namely oxalic acid (OA, 10 mM), desferrioxamine (DFA, 1 mM) or 2,2‧-bipyridyl (BPI, 1 mM). Element release from the glass into the solution after short term alteration (maximum 1 week) was measured by ICP-OES, and normalized mass losses and relative release ratios (with respect to Si) were evaluated for each element in each experimental condition. The presence of organic ligands had a significant effect on the dissolution of both glasses. Trivalent metals chelators (OA, DFA) impacted on the release of Fe3+ and Al3+, and thus on the global dissolution of both glasses, enhancing all release rates and dissolution stoichiometry (release rates were increased up to 7 times for Al or Fe). As expected, the mostly divalent metal chelator BPI interacted preferentially with Ca2+, Mg2+ and Fe2+. This study thus allows to highlight the central roles of iron and aluminium in interaction with some organic ligands in the alteration processes of basaltic glasses. It thus provides a step toward understanding the biological contribution of this fundamental geological process.

  9. [In vitro dissolution rate of Liuwei Wuling tablet based on biological potency and integrated dissolution].

    PubMed

    Zheng, Juan; Cheng, Ling; Shen, Cheng-ying; Li, Juan-juan; Qiu, Ling; Shen, Gang; Han, Jin; Yuan, Hai-long

    2015-11-01

    To explore the feasibility of chemical and biological method in evaluation of the in vitro dissolution rate of Liuwei Wuling tablet (LWT), this experiment investigated the inhibitory effect of LWT dissolving solutions on LX-2 hepatic stellate cells in 0.1% SDS dissolution medium in different dissolving periods. From these results, the cumulative dissolution rate of LWT was obtained based on the cell inhibitory rate. The dissolution rates of deoxyschizandrin, phillyrin, and Specnuezhenide were determined by HPLC method. A novel approach of self-defined weighting coefficient had been created to establish the integrated dissolution rate model. Then f2 similar factor method was used to evaluate the relevance of these two methods. The results showed that f2 values for deoxyschizandrin, phillyrin, Specnuezhenide, and the integrated dissolution were 61, 43, 61 and 75 respectively, indicating that the dissolution of multi-component integration could fully reflect the biological potency of the whole recipe. The dissolution evaluation method for multicomponent integration based on biological activity is expected to be one of the effective means for in vitro dissolution test of LWT. PMID:27097413

  10. A multiphase interfacial model for the dissolution of spent nuclear fuel

    NASA Astrophysics Data System (ADS)

    Jerden, James L.; Frey, Kurt; Ebert, William

    2015-07-01

    The Fuel Matrix Dissolution Model (FMDM) is an electrochemical reaction/diffusion model for the dissolution of spent uranium oxide fuel. The model was developed to provide radionuclide source terms for use in performance assessment calculations for various types of geologic repositories. It is based on mixed potential theory and consists of a two-phase fuel surface made up of UO2 and a noble metal bearing fission product phase in contact with groundwater. The corrosion potential at the surface of the dissolving fuel is calculated by balancing cathodic and anodic reactions occurring at the solution interfaces with UO2 and NMP surfaces. Dissolved oxygen and hydrogen peroxide generated by radiolysis of the groundwater are the major oxidizing agents that promote fuel dissolution. Several reactions occurring on noble metal alloy surfaces are electrically coupled to the UO2 and can catalyze or inhibit oxidative dissolution of the fuel. The most important of these is the oxidation of hydrogen, which counteracts the effects of oxidants (primarily H2O2 and O2). Inclusion of this reaction greatly decreases the oxidation of U(IV) and slows fuel dissolution significantly. In addition to radiolytic hydrogen, large quantities of hydrogen can be produced by the anoxic corrosion of steel structures within and near the fuel waste package. The model accurately predicts key experimental trends seen in literature data, the most important being the dramatic depression of the fuel dissolution rate by the presence of dissolved hydrogen at even relatively low concentrations (e.g., less than 1 mM). This hydrogen effect counteracts oxidation reactions and can limit fuel degradation to chemical dissolution, which results in radionuclide source term values that are four or five orders of magnitude lower than when oxidative dissolution processes are operative. This paper presents the scientific basis of the model, the approach for modeling used fuel in a disposal system, and preliminary

  11. Handling ligands with Coot

    PubMed Central

    Debreczeni, Judit É.; Emsley, Paul

    2012-01-01

    Coot is a molecular-graphics application primarily aimed to assist in model building and validation of biological macromolecules. Recently, tools have been added to work with small molecules. The newly incorporated tools for the manipulation and validation of ligands include interaction with PRODRG, subgraph isomorphism-based tools, representation of ligand chemistry, ligand fitting and analysis, and are described here. PMID:22505262

  12. DISSOLUTION OF FISSILE MATERIALS CONTAINING TANTALUM METAL

    SciTech Connect

    Rudisill, T; Mark Crowder, M; Michael Bronikowski, M

    2007-05-29

    The dissolution of composite materials containing plutonium (Pu) and tantalum (Ta) metals is currently performed in Phase I of the HB-Line facility. The conditions for the present flowsheet are the dissolution of 500 g of Pu metal in the 15 L dissolver using a 4 M nitric acid (HNO{sub 3}) solution containing 0.2 M potassium fluoride (KF) at 95 C for 4-6 h.[1] The Ta metal, which is essentially insoluble in HNO{sub 3}/fluoride solutions, is rinsed with process water to remove residual acid, and then burned to destroy classified information. During the initial dissolution campaign, the total mass of Pu and Ta in the dissolver charge was limited to nominally 300 g. The reduced amount of Pu in the dissolver charge coupled with significant evaporation of solution during processing of several dissolver charges resulted in the precipitation of a fluoride salt contain Pu. Dissolution of the salt required the addition of aluminum nitrate (Al(NO{sub 3}){sub 3}) and a subsequent undesired 4 h heating cycle. As a result of this issue, HB-Line Engineering requested the Savannah River National Laboratory (SRNL) to optimize the dissolution flowsheet to reduce the cycle time, reduce the risk of precipitating solids, and obtain hydrogen (H{sub 2}) generation data at lower fluoride concentrations.[2] Using samples of the Pu/Ta composite material, we performed three experiments to demonstrate the dissolution of the Pu metal using HNO{sub 3} solutions containing 0.15 and 0.175 M KF. When 0.15 M KF was used in the dissolving solution, 95.5% of the Pu in the sample dissolved in approximately 6 h. The undissolved material included a small amount of Pu metal and plutonium oxide (PuO{sub 2}) solids. Complete dissolution of the metal would have likely occurred if the dissolution time had been extended. This assumption is based on the steady increase in the Pu concentration observed during the last several hours of the experiment. We attribute the formation of PuO{sub 2} to the complexation

  13. Can the dissolution rates of individual minerals be used to describe whole rock dissolution?

    NASA Astrophysics Data System (ADS)

    Critelli, Teresa; Marini, Luigi; Schott, Jacques; Mavromatis, Vasileios; Apollaro, Carmine; Rinder, Thomas; De Rosa, Rosanna; Oelkers, Eric H.

    2014-05-01

    There have been an exhaustive number of laboratory studies determining the dissolution rates of individual minerals, but few have focused on the dissolution rates of minerals in multi-mineralic rocks. As a result, geochemical modeling of the temporal evolution of water-rock interaction is generally based on the assumption that the dissolution rate of minerals within a rock is equal to that measured in the laboratory on individual minerals. To verify this hypothesis, we have determined experimentally the dissolution rates of a well characterized metabasalt rock (Apollaro et al., 2011; Bloise et al., 2012) from the Mt. Reventino area (Southern Italy) at 25°C in mixed flow reactors. From these experiments and rock modal analysis we have deduced the dissolution rates of the minerals present in the rock (actinolite, albite, chlorite, epidote, and phengite). The major observation of this effort include: (i) only small differences in the dissolution rates of the individual minerals were observed; these rates are close to the whole-rock dissolution rate and (ii) the dissolution rates of albite and chlorite are in close agreement with laboratory rates obtained from individual mineral dissolution experiments, whereas those of actinolite, phengite, and epidote are not consistent with those reported in literature by 1-2 orders of magnitude. These results demonstrate that the dissolution rate of a given mineral in a multi-phase rock can be affected by the presence of the other minerals. Rock dissolution kinetics are likely constrained by the dissolution rates of the more abundant, lesser reactive mineral or minerals in the rock. These unreactive minerals can prevent the dissolution of the more rapidly dissolving mineral grains by keeping them out of contact with the aqueous phase. This implies that the overall weathering rate of rocks cannot be modelled from the measured dissolution rates of its individual minerals. If confirmed through further studies, this conclusion may

  14. Visualizing nanoparticle dissolution by imaging mass spectrometry.

    PubMed

    Szakal, Christopher; Ugelow, Melissa S; Gorham, Justin M; Konicek, Andrew R; Holbrook, R David

    2014-04-01

    We demonstrate the ability to visualize nanoparticle dissolution while simultaneously providing chemical signatures that differentiate between citrate-capped silver nanoparticles (AgNPs), AgNPs forced into dissolution via exposure to UV radiation, silver nitrate (AgNO3), and AgNO3/citrate deposited from aqueous solutions and suspensions. We utilize recently developed inkjet printing (IJP) protocols to deposit the different solutions/suspensions as NP aggregates and soluble species, which separate onto surfaces in situ, and collect mass spectral imaging data via time-of-flight secondary ion mass spectrometry (TOF-SIMS). Resulting 2D Ag(+) chemical images provide the ability to distinguish between the different Ag-containing starting materials and, when coupled with mass spectral peak ratios, provide information-rich data sets for quick and reproducible visualization of NP-based aqueous constituents. When compared to other measurements aimed at studying NP dissolution, the IJP-TOF-SIMS approach offers valuable information that can potentially help in understanding the complex equilibria in NP-containing solutions and suspensions, including NP dissolution kinetics and extent of overall dissolution. PMID:24611464

  15. Forsterite dissolution rates in Mg-sulfate-rich Mars-analog brines and implications of the aqueous history of Mars

    NASA Astrophysics Data System (ADS)

    Albright Olsen, Amanda; Hausrath, Elisabeth M.; Rimstidt, J. Donald

    2015-03-01

    High salinity brines, although rare on Earth's surface, may have been important in the geologic history of Mars. Increasing evidence suggests the importance of liquid brines in multiple locations on Mars. In order to interpret the effect of high ionic strength brines on olivine dissolution, which is widely present on Mars, 47 new batch reactor experiments combined with 35 results from a previous study conducted at 25°C from 1 < pH < 4 in magnesium sulfate, sodium sulfate, magnesium nitrate, and potassium nitrate solutions with ionic strengths as high as 12 m show that very high ionic strength brines have an inhibitory effect of forsterite dissolution rates. Multiple linear regression analysis of the data suggests that the inhibition in dissolution rates is due to decreased water activity at high ionic strengths. Regression models also show that mMg up to 4 m and mSO4 up to 3 m have no effect on forsterite dissolution rates. The effect of decreasing dissolution rates with decreasing aH2O is consistent with the idea that water acts as a ligand that participates in the dissolution process. Less available water to participate in the dissolution reaction results in a slower dissolution rate. Multiple linear regression analysis of the data produces the rate equation log r = -6.81 - 0.52pH + 3.26log aH2O. Forsterite in dilute solutions with a water activity of one dissolves twice as fast as those in brines with a water activity of 0.8.

  16. Influence of bulky yet flexible N-heterocyclic carbene ligands in gold catalysis.

    PubMed

    Collado, Alba; Patrick, Scott R; Gasperini, Danila; Meiries, Sebastien; Nolan, Steven P

    2015-01-01

    Three new Au(I) complexes of the formula [Au(NHC)(NTf2)] (NHC = N-heterocyclic carbene) bearing bulky and flexible ligands have been synthesised. The ligands studied are IPent, IHept and INon which belong to the 'ITent' ('Tent' for 'tentacular') family of NHC derivatives. The effect of these ligands in gold-promoted transformations has been investigated.

  17. Formation and dissolution of bacterial colonies

    NASA Astrophysics Data System (ADS)

    Weber, Christoph A.; Lin, Yen Ting; Biais, Nicolas; Zaburdaev, Vasily

    2015-09-01

    Many organisms form colonies for a transient period of time to withstand environmental pressure. Bacterial biofilms are a prototypical example of such behavior. Despite significant interest across disciplines, physical mechanisms governing the formation and dissolution of bacterial colonies are still poorly understood. Starting from a kinetic description of motile and interacting cells we derive a hydrodynamic equation for their density on a surface, where most of the kinetic coefficients are estimated from experimental data for N. gonorrhoeae bacteria. We use it to describe the formation of multiple colonies with sizes consistent with experimental observations. Finally, we show how the changes in the cell-to-cell interactions lead to the dissolution of the bacterial colonies. The successful application of kinetic theory to a complex far from equilibrium system such as formation and dissolution of living bacterial colonies potentially paves the way for the physical quantification of the initial stages of biofilm formation.

  18. Formation and dissolution of bacterial colonies.

    PubMed

    Weber, Christoph A; Lin, Yen Ting; Biais, Nicolas; Zaburdaev, Vasily

    2015-09-01

    Many organisms form colonies for a transient period of time to withstand environmental pressure. Bacterial biofilms are a prototypical example of such behavior. Despite significant interest across disciplines, physical mechanisms governing the formation and dissolution of bacterial colonies are still poorly understood. Starting from a kinetic description of motile and interacting cells we derive a hydrodynamic equation for their density on a surface, where most of the kinetic coefficients are estimated from experimental data for N. gonorrhoeae bacteria. We use it to describe the formation of multiple colonies with sizes consistent with experimental observations. Finally, we show how the changes in the cell-to-cell interactions lead to the dissolution of the bacterial colonies. The successful application of kinetic theory to a complex far from equilibrium system such as formation and dissolution of living bacterial colonies potentially paves the way for the physical quantification of the initial stages of biofilm formation.

  19. Criticality safety in high explosives dissolution

    SciTech Connect

    Troyer, S.D.

    1997-06-01

    In 1992, an incident occurred at the Pantex Plant in which the cladding around a fissile material component (pit) cracked during dismantlement of the high explosives portion of a nuclear weapon. Although the event did not result in any significant contamination or personnel exposures, concerns about the incident led to the conclusion that the current dismantlement process was unacceptable. Options considered for redesign, dissolution tooling design considerations, dissolution tooling design features, and the analysis of the new dissolution tooling are summarized. The final tooling design developed incorporated a number of safety features and provides a simple, self-contained, low-maintenance method of high explosives removal for nuclear explosive dismantlement. Analyses demonstrate that the tooling design will remain subcritical under normal, abnormal, and credible accident scenarios. 1 fig.

  20. Formation and dissolution of bacterial colonies.

    PubMed

    Weber, Christoph A; Lin, Yen Ting; Biais, Nicolas; Zaburdaev, Vasily

    2015-09-01

    Many organisms form colonies for a transient period of time to withstand environmental pressure. Bacterial biofilms are a prototypical example of such behavior. Despite significant interest across disciplines, physical mechanisms governing the formation and dissolution of bacterial colonies are still poorly understood. Starting from a kinetic description of motile and interacting cells we derive a hydrodynamic equation for their density on a surface, where most of the kinetic coefficients are estimated from experimental data for N. gonorrhoeae bacteria. We use it to describe the formation of multiple colonies with sizes consistent with experimental observations. Finally, we show how the changes in the cell-to-cell interactions lead to the dissolution of the bacterial colonies. The successful application of kinetic theory to a complex far from equilibrium system such as formation and dissolution of living bacterial colonies potentially paves the way for the physical quantification of the initial stages of biofilm formation. PMID:26465495

  1. DISSOLUTION OF IRRADIATED MURR FUEL ASSEMBLIES

    SciTech Connect

    Kyser, E.

    2010-06-17

    A literature survey on the dissolution of spent nuclear fuel from the University of Missouri Research Reactor (MURR) has been performed. This survey encompassed both internal and external literature sources for the dissolution of aluminum-clad uranium alloy fuels. The most limiting aspect of dissolution in the current facility configuration involves issues related to the control of the flammability of the off-gas from this process. The primary conclusion of this work is that based on past dissolution of this fuel in H-Canyon, four bundles of this fuel (initial charge) may be safely dissolved in a nitric acid flowsheet catalyzed with 0.002 M mercuric nitrate using a 40 scfm purge to control off-gas flammability. The initial charge may be followed by a second charge of up to five bundles to the same dissolver batch depending on volume and concentration constraints. The safety of this flowsheet relies on composite lower flammability limits (LFL) estimated from prior literature, pilot-scale work on the dissolution of site fuels, and the proposed processing flowsheet. Equipment modifications or improved LFL data offer the potential for improved processing rates. The fuel charging sequence, as well as the acid and catalyst concentrations, will control the dissolution rate during the initial portion of the cycle. These parameters directly impact the hydrogen and off-gas generation and, along with the purge flowrate determine the number of bundles that may be charged. The calculation approach within provides Engineering a means to determine optimal charging patterns. Downstream processing of this material should be similar to that of recent processing of site fuels requiring only minor adjustments of the existing flowsheet parameters.

  2. Ligand modeling and design

    SciTech Connect

    Hay, B.P.

    1997-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used in the cost-effective removal of specific radionuclides from nuclear waste streams. Organic ligands with metal ion specificity are critical components in the development of solvent extraction and ion exchange processes that are highly selective for targeted radionuclides. The traditional approach to the development of such ligands involves lengthy programs of organic synthesis and testing, which in the absence of reliable methods for screening compounds before synthesis, results in wasted research effort. The author`s approach breaks down and simplifies this costly process with the aid of computer-based molecular modeling techniques. Commercial software for organic molecular modeling is being configured to examine the interactions between organic ligands and metal ions, yielding an inexpensive, commercially or readily available computational tool that can be used to predict the structures and energies of ligand-metal complexes. Users will be able to correlate the large body of existing experimental data on structure, solution binding affinity, and metal ion selectivity to develop structural design criteria. These criteria will provide a basis for selecting ligands that can be implemented in separations technologies through collaboration with other DOE national laboratories and private industry. The initial focus will be to select ether-based ligands that can be applied to the recovery and concentration of the alkali and alkaline earth metal ions including cesium, strontium, and radium.

  3. Microbial dissolution of silicate materials. Final report

    SciTech Connect

    Schwartzman, D.

    1996-03-26

    The objective of this research was to better understand the role of selected thermophilic bacteria in the colonization and dissolution of silicate minerals, with potential applications to the HDR Project. The demonstration of enhanced dissolution from microbial effects is critically dependent on providing a mineral bait within a media deficient in the critical nutrient found in the mineral (e.g., Fe). Reproducible experimental conditions in batch experiments require agitation to expose mineral powders, as well as nearly similar initial conditions for both inoculated cultures and controls. It is difficult, but not impossible to ensure reproducible conditions with microbes favoring filamentous growth habits.

  4. Saltcake dissolution FY 1998 status report

    SciTech Connect

    HERTING, D.L.

    1999-05-18

    A laboratory scouting study was completed on the dissolution characteristics of Hanford waste from three single-shell waste tanks: 241-BY-102, 241-BY-106, and 241-B-106. Gross dissolution behavior (percent undissolved solids as a function of dilution) is explained in terms of characteristics of individual salts in the waste. The percentage of the sodium inventory retrievable from the tanks by dissolving saltcake at reasonable dilution levels is estimated at 86% of the total sodium for tank BY-102, 98% for BY-106, and 79% for B-106.

  5. Nontronite dissolution rates and implications for Mars

    NASA Astrophysics Data System (ADS)

    Gainey, S. R.; Hausrath, E. M.; Hurowitz, J. A.; Milliken, R. E.

    2014-02-01

    The Fe-rich smectite nontronite M+1.05[Si6.98Al1.02][Al0.29Fe3.68Mg0.04]O20(OH)4 has been detected using orbital data at multiple locations in ancient terrains on Mars, including Mawrth Vallis, Nilli Fossae, north of the Syrtis Major volcanic plateau, Terra Meridiani, and the landing site of the Mars Science Laboratory (MSL), Gale Crater. Given the antiquity of these sites (>3.0 Ga), it is likely that nontronite has been exposed to the martian environment for long periods of time and therefore provides an integrated record of processes in near surface environments including pedogenesis and diagenesis. In particular, nontronite detected at Mawrth Vallis is overlain by montmorillonite and kaolinite, and it has been previously suggested that this mineralogical sequence may be the result of surface weathering. In order to better understand clay mineral weathering on Mars, we measured dissolution rates of nontronite in column reactors at solution pH values of 0.9, 1.7, and 3.0, and two flow rates (0.16 ml/h and 0.32 ml/h). Solution chemistry indicates stoichiometric dissolution at pH = 0.9 and non-stoichiometric dissolution at pH = 1.7 and 3.0. Mineral dissolution rates based on elemental release rates at pH = 1.7 and 3.0 of Ca, Si and Fe follow the order interlayer > tetrahedral > octahedral sites, respectively. The behavior of all experiments suggests far from equilibrium conditions, with the exception of the experiment performed at pH 3.0 and flow rate 0.16 ml/h. A pH-dependent dissolution rate law was calculated through Si release from experiments that showed no dependence on saturation (far from equilibrium conditions) under both flow rates and is r = 10-12.06 (±0.123) · 10-0.297 (±0.058)·pH where r has the units mol mineral m-2 s-1. When compared to dissolution rates from the literature, our results indicate that nontronite dissolution is significantly slower than dissolution of the primary phases present in basalt under acidic conditions, suggesting that once

  6. Effects of magnetic fields on dissolution of arthritis causing crystals

    NASA Astrophysics Data System (ADS)

    Takeuchi, Y.; Iwasaka, M.

    2015-05-01

    The number of gout patients has rapidly increased because of excess alcohol and salt intake. The agent responsible for gout is the monosodium urate (MSU) crystal. MSU crystals are found in blood and consist of uric acid and sodium. As a substitute for drug dosing or excessive water intake, physical stimulation by magnetic fields represents a new medical treatment for gout. In this study, we investigated the effects of a magnetic field on the dissolution of a MSU crystal suspension. The white MSU crystal suspension was dissolved in an alkaline solution. We measured the light transmission of the MSU crystal suspension by a transmitted light measuring system. The magnetic field was generated by a horizontal electromagnet (maximum field strength was 500 mT). The MSU crystal suspension that dissolved during the application of a magnetic field of 500 mT clearly had a higher dissolution rate when compared with the control sample. We postulate that the alkali solution promoted penetration upon diamagnetic rotation and this magnetic field orienting is because of the pronounced diamagnetic susceptibility anisotropy of the MSU crystal. The results indicate that magnetic fields represent an effective gout treatment approach.

  7. Ligand modeling and design

    SciTech Connect

    Hay, B.

    1996-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used tin applications for the cost-effective removal of specific radionuclides from nuclear waste streams.

  8. Natural remobilization of multicomponent DNAPL pools due to dissolution.

    PubMed

    Roy, J W; Smith, J E; Gillham, R W

    2002-12-01

    Mixtures of dense nonaqueous phase liquids (DNAPLs) trapped in the subsurface can act as long-term sources of contamination by dissolving into flowing groundwater. If the components have different solubilities then dissolution will alter the composition of the remaining DNAPL. We theorized that a multicomponent DNAPL pool may become mobile due to the natural dissolution process. In this study, we focused on two scenarios: (1) a DNAPL losing light component(s), with the potential for downward migration; and (2) a DNAPL losing dense component(s), with the potential for upward migration following transformation into a less dense than water nonaqueous phase liquid (LNAPL). We considered three binary mixtures of common groundwater contaminants: benzene and tetrachloroethylene (PCE), PCE and dichloromethane (DCM), and DCM and toluene. A number of physical properties that control the retention and transport of DNAPL in porous media were measured for the mixtures, namely: density, interfacial tension, effective solubility, and viscosity. All properties except density exhibited nonlinear relationships with changing molar ratio of the DNAPL. To illustrate the potential for natural remobilization, we modelled the following two primary mechanisms: the reduction in pool height as mass is lost by dissolution, and the changes in fluid properties with changing molar ratio of the DNAPL. The first mechanism always reduces the capillary pressure in the pool, while the second mechanism may increase the capillary pressure or alter the direction of the driving force. The difference between the rate of change of each determines whether the potential for remobilization increases or decreases. Static conditions and horizontal layering were assumed along with a one-dimensional, compositional modelling approach. Our results indicated that for initial benzene/PCE ratios greater than 25:75, the change in density was sufficiently faster than the decline in pool height to promote DNAPL

  9. Bioenhancement of NAPL pool dissolution: experimental evaluation

    NASA Astrophysics Data System (ADS)

    Seagren, Eric A.; Rittmann, Bruce E.; Valocchi, Albert J.

    2002-03-01

    Experiments were conducted to quantify nonaqueous phase liquid (NAPL) pool dissolution and its enhancement by in situ biodegradation. The experiments were performed using square cross-section, glass-bead packed column reactors with a small pool of a toluene-in-dodecane mixture (toluene mole fraction, Xtol≈0.02 or 0.09). Experimental quasi-steady-state toluene dissolution fluxes were determined using a 14C-carbon mass-balance approach during water flushing with and without biodegradation. The experiments demonstrated a statistically significant bioenhancement of the toluene dissolution flux of up to roughly twofold at average pore water velocities of approximately 0.1 and 1 m/day when the toluene mole fraction was low (≈0.02); however, little or no bioenhancement was observed with the higher mole fraction (≈0.09). Although it cannot be determined conclusively, the weight of evidence based on biomass measurements and model analyses suggests that the reduced bioenhancement for the high mole fraction was due to higher dissolved toluene concentrations, which may have caused toxicity effects. Importantly, even though NAPL dissolution was not bioenhanced in every case, the biodegradation reduced toluene concentrations to low levels in the reactor effluents.

  10. Dilution physics modeling: Dissolution/precipitation chemistry

    SciTech Connect

    Onishi, Y.; Reid, H.C.; Trent, D.S.

    1995-09-01

    This report documents progress made to date on integrating dilution/precipitation chemistry and new physical models into the TEMPEST thermal-hydraulics computer code. Implementation of dissolution/precipitation chemistry models is necessary for predicting nonhomogeneous, time-dependent, physical/chemical behavior of tank wastes with and without a variety of possible engineered remediation and mitigation activities. Such behavior includes chemical reactions, gas retention, solids resuspension, solids dissolution and generation, solids settling/rising, and convective motion of physical and chemical species. Thus this model development is important from the standpoint of predicting the consequences of various engineered activities, such as mitigation by dilution, retrieval, or pretreatment, that can affect safe operations. The integration of a dissolution/precipitation chemistry module allows the various phase species concentrations to enter into the physical calculations that affect the TEMPEST hydrodynamic flow calculations. The yield strength model of non-Newtonian sludge correlates yield to a power function of solids concentration. Likewise, shear stress is concentration-dependent, and the dissolution/precipitation chemistry calculations develop the species concentration evolution that produces fluid flow resistance changes. Dilution of waste with pure water, molar concentrations of sodium hydroxide, and other chemical streams can be analyzed for the reactive species changes and hydrodynamic flow characteristics.

  11. 12 CFR 546.4 - Voluntary dissolution.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... accounts or in exchange for that association's payment of all the association's outstanding obligations and... 12 Banks and Banking 5 2011-01-01 2011-01-01 false Voluntary dissolution. 546.4 Section 546.4 Banks and Banking OFFICE OF THRIFT SUPERVISION, DEPARTMENT OF THE TREASURY FEDERAL MUTUAL...

  12. Dissolution Treatment of Depleted Uranium Waste

    SciTech Connect

    Gates-Anderson, D D; Laue, C A; Fitch, T E

    2004-02-09

    Researchers at LLNL have developed a 3-stage process that converts pyrophoric depleted uranium metal turnings to a solidified final product that can be transported to and buried at a permitted land disposal site. The three process stages are: (1) pretreatment; (2) dissolution; and (3) solidification. Each stage was developed following extensive experimentation. This report presents the results of their experimental studies.

  13. 25 CFR 11.605 - Dissolution.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... dissolution of marriage if: (1) The court finds that the marriage is irretrievably broken, if the finding is... affecting the attitude of one or both of the parties towards the marriage; (2) The court finds that either..., or provided for child custody, the support of any child entitled to support, the maintenance...

  14. Dissolution enhancement of chlorzoxazone using cogrinding technique

    PubMed Central

    Raval, Mihir K.; Patel, Jaydeep M.; Parikh, Rajesh K.; Sheth, Navin R.

    2015-01-01

    Purpose: The aim of the present work was to improve rate of dissolution and processing parameters of BCS class II drug, chlorzoxazone using cogrinding technique in the presence of different excipients as a carrier. Materials and Methods: The drug was coground with various carriers like polyethylene glycol (PEG 4000), hydroxypropyl methylcellulose (HPMC) E50LV, polyvinylpyrrolidone (PVP)K30, Kaolin and Neusilin US2 using ball mill, where only PEG 4000 improved dissolution rate of drug by bringing amorphization in 1:3 ratio. The coground mixture after 3 and 6 h was evaluated for various analytical, physicochemical and mechanical parameters. Results: The analysis showed conversion of Chlorzoxazone from its crystalline to amorphization form upon grinding with PEG 4000. Coground mixture as well as its directly compressed tablet showed 2.5-fold increment in the dissolution rate compared with pure drug. Directly compressible tablets prepared from pure drug required a large quantity of microcrystalline cellulose (MCC) during compression. The coground mixture and formulation was found stable in nature even after storage (40°C/75% relative humidity). Conclusions: Cogrinding can be successfully utilized to improve the rate of dissolution of poorly water soluble drugs and hence bioavailability. PMID:26682195

  15. On the dissolution of iridium by aluminum.

    SciTech Connect

    Hewson, John C.

    2009-08-01

    The potential for liquid aluminum to dissolve an iridium solid is examined. Substantial uncertainties exist in material properties, and the available data for the iridium solubility and iridium diffusivity are discussed. The dissolution rate is expressed in terms of the regression velocity of the solid iridium when exposed to the solvent (aluminum). The temperature has the strongest influence in the dissolution rate. This dependence comes primarily from the solubility of iridium in aluminum and secondarily from the temperature dependence of the diffusion coefficient. This dissolution mass flux is geometry dependent and results are provided for simplified geometries at constant temperatures. For situations where there is negligible convective flow, simple time-dependent diffusion solutions are provided. Correlations for mass transfer are also given for natural convection and forced convection. These estimates suggest that dissolution of iridium can be significant for temperatures well below the melting temperature of iridium, but the uncertainties in actual rates are large because of uncertainties in the physical parameters and in the details of the relevant geometries.

  16. Efavirenz Dissolution Enhancement I: Co-Micronization

    PubMed Central

    da Costa, Maíra Assis; Seiceira, Rafael Cardoso; Rodrigues, Carlos Rangel; Hoffmeister, Cristiane Rodrigues Drago; Cabral, Lucio Mendes; Rocha, Helvécio Vinícius Antunes

    2012-01-01

    AIDS constitutes one of the most serious infectious diseases, representing a major public health priority. Efavirenz (EFV), one of the most widely used drugs for this pathology, belongs to the Class II of the Biopharmaceutics Classification System for drugs with very poor water solubility. To improve EFV’s dissolution profile, changes can be made to the physical properties of the drug that do not lead to any accompanying molecular modifications. Therefore, the study objective was to develop and characterize systems with efavirenz able to improve its dissolution, which were co-processed with sodium lauryl sulfate (SLS) and polyvinylpyrrolidone (PVP). The technique used was co-micronization. Three different drug:excipient ratios were tested for each of the two carriers. The drug dispersion dissolution results showed significant improvement for all the co-processed samples in comparison to non-processed material and corresponding physical mixtures. The dissolution profiles obtained for dispersion with co-micronized SLS samples proved superior to those of co-micronized PVP, with the proportion (1:0.25) proving the optimal mixture. The improvements may be explained by the hypothesis that formation of a hydrophilic layer on the surface of the micronized drug increases the wettability of the system formed, corroborated by characterization results indicating no loss of crystallinity and an absence of interaction at the molecular level. PMID:24300394

  17. 25 CFR 11.605 - Dissolution.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... dissolution of marriage if: (1) The court finds that the marriage is irretrievably broken, if the finding is... affecting the attitude of one or both of the parties towards the marriage; (2) The court finds that either... of marriage, the Court of Indian Offenses shall grant the decree in that form unless the other...

  18. 25 CFR 11.605 - Dissolution.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... dissolution of marriage if: (1) The court finds that the marriage is irretrievably broken, if the finding is... affecting the attitude of one or both of the parties towards the marriage; (2) The court finds that either... of marriage, the Court of Indian Offenses shall grant the decree in that form unless the other...

  19. 25 CFR 11.605 - Dissolution.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... dissolution of marriage if: (1) The court finds that the marriage is irretrievably broken, if the finding is... affecting the attitude of one or both of the parties towards the marriage; (2) The court finds that either... of marriage, the Court of Indian Offenses shall grant the decree in that form unless the other...

  20. 25 CFR 11.605 - Dissolution.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... dissolution of marriage if: (1) The court finds that the marriage is irretrievably broken, if the finding is... affecting the attitude of one or both of the parties towards the marriage; (2) The court finds that either... of marriage, the Court of Indian Offenses shall grant the decree in that form unless the other...

  1. Time-Related Determinants of Marital Dissolution.

    ERIC Educational Resources Information Center

    Heaton, Tim B.

    1991-01-01

    Examined temporal dimensions (timing of prior events, historical time, duration dependence, selectivity) and their impact on marital dissolution in multivariate continuous time model using data from June 1985 Current Population Survey. Results indicated that marital stability decreased over time, increased over marital duration, increased with age…

  2. Effect of background electrolytes on gypsum dissolution

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    Knowledge of the dissolution behaviour of gypsum (CaSO4· 2H2O) in aqueous solutions is of primary importance in many natural and technological processes (Pachon-Rodriguez and Colombani, 2007), including the weathering of rocks and gypsum karst formations, deformation of gypsum-bearing rocks, the quality of drinking water, amelioration of soil acidity, scale formation in the oil and gas industry or measurement of water motion in oceanography. Specific ions in aqueous solutions can play important but very different roles on mineral dissolution. For example, the dissolution rates and the morphology of dissolution features may be considerably modified by the presence of the foreign ions in the solution, which adsorb at the surface and hinder the detachment of the ions building the crystal. Dissolution processes in the aqueous environment are closely related to the rearrangement of water molecules around solute ions and the interaction between the solvent molecules themselves. The rearrangement of water molecules with respect to solute species has been recognized as the main kinetic barrier for crystal dissolution in many systems (Davis, 2000; De Yoreo and Dove 2004; Wasylenki et al. 2005). Current research suggest that the control that electrolytes exert on water structure is limited to the local environment surrounding the ions and is not related to long-range electric fields emanating from the ions but results from effects associated with the hydration shell(s) of the ions (Collins et al. 2007) and the ions' capacity to break or structure water (i.e. chaotropic and kosmotropic ions, respectively). These effects will ultimately affect the kinetics of crystal dissolution, and could be correlated with the water affinity of the respective background ions following a trend known as the lyotropic or Hofmeister series (Kunz et al. 2004; Dove and Craven, 2005). In situ macroscopic and Atomic Force Microscopy (AFM) flow-through dissolution experiments were conducted at a

  3. Surfactant dissolution and mobilization of LNAPL contaminants in aquifers.

    PubMed

    Chevalier, Lizette R

    2003-05-01

    Improper disposal, accidental spills and leaks of non-aqueous phase liquids (NAPL) such as gasoline, fuel oil and creosote result in long-term persistent sources of groundwater pollution. Column and 2-D tanks experiments were conducted to evaluate the use of surfactant-enhanced recovery of light non-aqueous phase liquids (LNAPL) in groundwater aquifers. These experiments focused on the use of surfactants to promote dissolution and mobilization in addition to evaluating the increase of aqueous phase permeability as residual NAPL is recovered. Further experiments are presented that show the innovative use of surfactants during primary pumping to recover free product can potentially increase the amount of free product recovered, can potentially reduce the amount of residual NAPL remaining after primary pumping and performs better than the use of surfactants to mobilize trapped residual NAPL.

  4. In vitro Dissolution Studies on Solid Dispersions of Mefenamic Acid

    PubMed Central

    Rao, K. R. S. Sambasiva; Nagabhushanam, M V; Chowdary, K. P. R.

    2011-01-01

    Solid dispersions of mefanamic acid with a water-soluble polymer polyvinyl pyrrolidine and a super disintegrant, primojel were prepared by common solvent and solvent evaporation methods employing methanol as the solvent. The dissolution rate and dissolution efficiency of the prepared solid dispersions were evaluated in comparison to the corresponding pure drug. Solid dispersions of mefenamic acid showed a marked enhancement in dissolution rate and dissolution efficiency. At 1:4 ratio of mefenamic acid-primojel a 2.61 fold increase in the dissolution rate of mefenamic acid was observed with solid dispersion. The solid dispersions in combined carriers gave much higher rates of dissolution than super disintegrants alone. Mefanamic acid-primojel-polyvinyl pyrrolidine (1:3.2:0.8) solid dispersion gave a 4.11 fold increase in the dissolution rate of mefenamic acid. Super disintegrants alone or in combination with polyvinyl pyrrolidine could be used to enhance the dissolution rate of mefenamic acid. PMID:22303074

  5. Melanoma cell galectin-1 ligands functionally correlate with malignant potential*

    PubMed Central

    Yazawa, Erika M.; Geddes-Sweeney, Jenna E.; Cedeno-Laurent, Filiberto; Walley, Kempland C.; Barthel, Steven R.; Opperman, Matthew J.; Liang, Jennifer; Lin, Jennifer Y.; Schatton, Tobias; Laga, Alvaro C.; Mihm, Martin C.; Qureshi, Abrar A.; Widlund, Hans R.; Murphy, George F.; Dimitroff, Charles J.

    2015-01-01

    Galectin-1 (Gal-1)-binding to Gal-1 ligands on immune and endothelial cells can influence melanoma development through dampening anti-tumor immune responses and promoting angiogenesis. However, whether Gal-1 ligands are functionally expressed on melanoma cells to help control intrinsic malignant features remains poorly understood. Here, we analyzed expression, identity and function of Gal-1 ligands in melanoma progression. Immunofluorescent analysis of benign and malignant human melanocytic neoplasms revealed that Gal-1 ligands were abundant in severely-dysplastic nevi as well as in primary and metastatic melanomas. Biochemical assessments indicated that melanoma cell adhesion molecule (MCAM) was a major Gal-1 ligand on melanoma cells that was largely dependent on its N-glycans. Other melanoma cell Gal-1 ligand activity conferred by O-glycans was negatively regulated by α2,6 sialyltransferase ST6GalNAc2. In Gal-1-deficient mice, MCAM-silenced (MCAMKD) or ST6GalNAc2-overexpressing (ST6O/E) melanoma cells exhibited slower growth rates, underscoring a key role for melanoma cell Gal-1 ligands and host Gal-1 in melanoma growth. Further analysis of MCAMKD or ST6O/E melanoma cells in cell migration assays indicated that Gal-1 ligand-dependent melanoma cell migration was severely inhibited. These findings provide a refined perspective on Gal-1 – melanoma cell Gal-1 ligand interactions as contributors to melanoma malignancy. PMID:25756799

  6. Dissolution Kinetics of Biogenic Magnesian Calcites

    NASA Astrophysics Data System (ADS)

    Thompson, R.; Guidry, M.; Mackenzie, F. T.; De Carlo, E. H.

    2014-12-01

    Ocean acidification (OA) is a serious concern for the health of calcifying ecosystems in the near future. During the past century, surface ocean pH has decreased by ~0.1 pH units, and is expected to decrease further by 0.3-0.4 pH units by the end of this century. The process of OA will likely result in both decreased calcification rates and increased rates of carbonate mineral dissolution, particularly involving the magnesian calcite (Mg-calcite) calcifiers found in shallow-water reef and other carbonate environments. Many Mg-calcite compositions are the most soluble of the carbonate phases commonly found in reef environments (often comprising much of the cementation and structure within a reef), and are therefore potentially the most susceptible to dissolution processes associated with OA. However, the dissolution kinetics of these phases is poorly known, limiting our ability to understand their behavior in nature. Laboratory experiments designed to investigate the mechanisms and dissolution rates of biogenic Mg-calcite mineral phases in distilled water and seawater over a range of CO2 and T conditions were conducted employing both batch and fluidized-bed reactor systems and using a variety of cleaned and annealed biogenic Mg-calcite phases. Our initial results have shown that the dissolution rate at 298 K and a pCO2 of ~350 ppm of the crustose coralline alga Amphiroa rigida (~20 mol% MgCO3) in seawater undersaturated with respect to this phase is 3.6 μmol g-1 hr-1, nearly 50% greater than that under similar conditions for aragonite. This rate and the derived experimental rate law are consistent with the preliminary findings of Walter and Morse (1985). Additional kinetic (and also solubility) data will be presented for the following species: Chiton tuberculatus (~0-4 mol% MgCO3); Echinometra mathei and/or Lytechinus variegatus (~8-12 mol% MgCO3); Homotrema rubrum (12-16 mol% MgCO3); and Lithothamnion sp. (~18-24 mol% MgCO3). Quantification of the rates of

  7. Modeling NAPL dissolution fingering with upscaled mass transfer rate coefficients

    NASA Astrophysics Data System (ADS)

    Imhoff, Paul T.; Farthing, Matthew W.; Miller, Cass T.

    2003-10-01

    The dissolution of nonaqueous phase liquids (NAPLs) at residual saturation in porous media has sometimes resulted in the development of preferential dissolution pathways or NAPL dissolution fingers. While NAPL dissolution fingering may be modeled using numerical simulators with fine discretization, this approach is computational intensive. We derived an expression for an upscaled mass transfer rate coefficient that accounts for the growth of dissolution fingers within porous media contaminated uniformly with residual NAPL. This expression was closely related to the lengthening of the dissolution front. Data from physical experiments and numerical simulations in two dimensions were used to examine the growth of the dissolution front and the corresponding upscaled mass transfer rate coefficient. Using this upscaled mass transfer rate coefficient, the time when dissolution fingering results in a reduction in the overall mass transfer rate and thus controls the rate of NAPL dissolution was determined. This crossover time is a convenient parameter for assessing the influence of dissolution fingering on NAPL removal. For the physical experiments and numerical simulations analyzed in this study, the crossover time to dissolution fingering control always occurred before the dissolution front had moved 14 cm within NAPL-contaminated porous media, which is small compared to the scale of typical systems of concern. To verify the utility of this approach, data from a three-dimensional physical experiment were predicted reasonably well using an upscaled mass transfer rate coefficient that was determined independently from this experiment.

  8. RELATIVE DISSOLUTION RATES OF RADIOACTIVE MATERIALS USED AT AWE.

    PubMed

    Miller, T J; Bingham, D; Cockerill, R; Waldren, S; Moth, N

    2016-09-01

    A simple in vitro dissolution test was used to provide a semi-quantitative comparison of the relative dissolution rates of samples of radioactive materials used at Atomic Weapons Establishment in a lung fluid surrogate (Ringer's solution). A wide range of dissolution rates were observed for aged legacy actinides, freshly produced actinide alloys and actinides from waste management operations.

  9. Examining Two Types of Best Friendship Dissolution during Early Adolescence

    ERIC Educational Resources Information Center

    Bowker, Julie C.

    2011-01-01

    This study examined young adolescents' experiences with best friendship dissolution. Participants were 77 sixth-grade students (M age = 11.63 years, SD = 0.36; 11.00-12.69 age range) who reported on past experiences with (1) "complete dissolutions" (when friendship ties are completely severed), and (2) "downgrade dissolutions" (when the best…

  10. Ego-Dissolution and Psychedelics: Validation of the Ego-Dissolution Inventory (EDI)

    PubMed Central

    Nour, Matthew M.; Evans, Lisa; Nutt, David; Carhart-Harris, Robin L.

    2016-01-01

    Aims: The experience of a compromised sense of “self”, termed ego-dissolution, is a key feature of the psychedelic experience. This study aimed to validate the Ego-Dissolution Inventory (EDI), a new 8-item self-report scale designed to measure ego-dissolution. Additionally, we aimed to investigate the specificity of the relationship between psychedelics and ego-dissolution. Method: Sixteen items relating to altered ego-consciousness were included in an internet questionnaire; eight relating to the experience of ego-dissolution (comprising the EDI), and eight relating to the antithetical experience of increased self-assuredness, termed ego-inflation. Items were rated using a visual analog scale. Participants answered the questionnaire for experiences with classical psychedelic drugs, cocaine and/or alcohol. They also answered the seven questions from the Mystical Experiences Questionnaire (MEQ) relating to the experience of unity with one’s surroundings. Results: Six hundred and ninety-one participants completed the questionnaire, providing data for 1828 drug experiences (1043 psychedelics, 377 cocaine, 408 alcohol). Exploratory factor analysis demonstrated that the eight EDI items loaded exclusively onto a single common factor, which was orthogonal to a second factor comprised of the items relating to ego-inflation (rho = −0.110), demonstrating discriminant validity. The EDI correlated strongly with the MEQ-derived measure of unitive experience (rho = 0.735), demonstrating convergent validity. EDI internal consistency was excellent (Cronbach’s alpha 0.93). Three analyses confirmed the specificity of ego-dissolution for experiences occasioned by psychedelic drugs. Firstly, EDI score correlated with drug-dose for psychedelic drugs (rho = 0.371), but not for cocaine (rho = 0.115) or alcohol (rho = −0.055). Secondly, the linear regression line relating the subjective intensity of the experience to ego-dissolution was significantly steeper for psychedelics

  11. The Dissolution of an Interfween Miscible Liquids

    NASA Technical Reports Server (NTRS)

    Vlad, D.H.; Maher, J.V.

    1999-01-01

    The disappearance of the surface tension of the interface of a binary mixture, measured using the dynamic surface light scattering technique, is slower for a binary mixture of higher density contrast. A comparison with a naive diffusion model, expected to provide a lower limit for the speed of dissolution in the absence of gravity shows that the interfacial surface tension disappears much slower than even by diffusion with the effect becoming much more pronounced when density contrast between the liquid phases is increased. Thus, the factor most likely to be responsible for this anomalously slow dissolution is gravity. A mechanism could be based on the competition between diffusive relaxation and sedimentation at the dissolving interface.

  12. A morpholinium ionic liquid for cellulose dissolution.

    PubMed

    Raut, Dilip G; Sundman, Ola; Su, Weiqing; Virtanen, Pasi; Sugano, Yasuhito; Kordas, Krisztian; Mikkola, Jyri-Pekka

    2015-10-01

    A series of substituted morpholinium ionic salts and allyl ammonium acetates were prepared. Amongst those, N-allyl-N-methylmorpholinium acetate ([AMMorp][OAc]) was found to dissolve cellulose readily without any pre-processing of native cellulose. At 120°C, [AMMorp][OAc] could dissolve 30 wt%, 28 wt% and 25 wt% of cellulose with degree of polymerization (DPn) - 789, 1644 and 2082 respectively, in 20 min. Importantly, SEC analysis indicated that no discernible changes occurred in terms of the degree of polymerization of the different celluloses after regeneration. Furthermore, when comparing the cellulose dissolution capability of these newly synthesized ionic liquids, it is evident that the combination of all three constituents - the morpholinium cation, the existence of an allyl group and choosing the acetate anion are essential for efficient cellulose dissolution. The structure and morphology of the regenerated cellulosic materials were characterized by SEM, XRD, TGA, CP/MAS (13)C NMR and FTIR, respectively. PMID:26076596

  13. Uranium-Molybdenum Dissolution Flowsheet Studies

    SciTech Connect

    Pierce, R. A.

    2007-03-01

    The Super Kukla (SK) Prompt Burst Reactor operated at the Nevada Test Site from 1964 to 1978. The SK material is a uranium-molybdenum (U-Mo) alloy material of 90% U/10% Mo by weight at approximately 20% 235U enrichment. H-Canyon Engineering (HCE) requested that the Savannah River National Lab (SRNL) define a flowsheet for safely and efficiently dissolving the SK material. The objective is to dissolve the material in nitric acid (HNO3) in the H-Canyon dissolvers to a U concentration of 15-20 g/L (3-4 g/L 235U) without the formation of precipitates or the generation of a flammable gas mixture. Testing with SK material validated the applicability of dissolution and solubility data reported in the literature for various U and U-Mo metals. Based on the data, the SK material can be dissolved in boiling 3.0-6.0 M HNO3 to a U concentration of 15-20 g/L and a corresponding Mo concentration of 1.7-2.2 g/L. The optimum flowsheet will use 4.0-5.0 M HNO3 for the starting acid. Any nickel (Ni) cladding associated with the material will dissolve readily. After dissolution is complete, traditional solvent extraction flowsheets can be used to recover and purify the U. Dissolution rates for the SK material are consistent with those reported in the literature and are adequate for H-Canyon processing. When the SK material dissolved at 70-100 o C in 1-6 M HNO3, the reaction bubbled vigorously and released nitrogen oxide (NO) and nitrogen dioxide (NO2) gas. Gas generation tests in 1 M and 2 M HNO3 at 100 o C generated less than 0.1 volume percent hydrogen (H2) gas. It is known that higher HNO3 concentrations are less favorable for H2 production. All tests at 70-100 o C produced sufficient gas to mix the solutions without external agitation. At room temperature in 5 M HNO3, the U-Mo dissolved slowly and the U-laden solution sank to the bottom of the dissolution vessel because of its greater density. The effect of the density difference insures that the SK material cannot dissolve and

  14. A morpholinium ionic liquid for cellulose dissolution.

    PubMed

    Raut, Dilip G; Sundman, Ola; Su, Weiqing; Virtanen, Pasi; Sugano, Yasuhito; Kordas, Krisztian; Mikkola, Jyri-Pekka

    2015-10-01

    A series of substituted morpholinium ionic salts and allyl ammonium acetates were prepared. Amongst those, N-allyl-N-methylmorpholinium acetate ([AMMorp][OAc]) was found to dissolve cellulose readily without any pre-processing of native cellulose. At 120°C, [AMMorp][OAc] could dissolve 30 wt%, 28 wt% and 25 wt% of cellulose with degree of polymerization (DPn) - 789, 1644 and 2082 respectively, in 20 min. Importantly, SEC analysis indicated that no discernible changes occurred in terms of the degree of polymerization of the different celluloses after regeneration. Furthermore, when comparing the cellulose dissolution capability of these newly synthesized ionic liquids, it is evident that the combination of all three constituents - the morpholinium cation, the existence of an allyl group and choosing the acetate anion are essential for efficient cellulose dissolution. The structure and morphology of the regenerated cellulosic materials were characterized by SEM, XRD, TGA, CP/MAS (13)C NMR and FTIR, respectively.

  15. Dissolution of lead paint in aqueous solutions

    SciTech Connect

    Barnes, G.L.; Davis, A.P.

    1996-07-01

    An analysis of the rate and extent of lead leaching from a lead-based paint was completed. At low-solution pH, dissolution was rapid and approached 80% of the total lead. Residual lead can be estimated based on the predicted solubility of lead carbonate and basic lead carbonate. Release of lead from the paint was slower than that from pure basic lead carbonate due to inhibition by the paint matrix. Although the dissolved concentration of lead in solution at neutral/high pH was low, the paint binder was apparently destroyed at these pH values, releasing colloidal lead pigment particles. The presence of ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) enhanced both the rate and degree of lead dissolution, while benzoic acid had a minimal effect.

  16. Saltcake Dissolution FY 2000 Status Report

    SciTech Connect

    HERTING, D.L.

    2000-09-27

    Laboratory tests were completed on the dissolution characteristics of Hanford saltcake waste from single-shell waste tanks 241-TX- 113, 241-BY-102, 241-BY-106, 241-A-101, and 241-S-102 (henceforth referred to as TX-113, BY-102, BY-106, A-101, and S-102, respectively). This work was funded by the Tanks Focus Area (EM-50) under Technical Task Plan Number RL0-8-WT-41, ''PHMC Pretreatment--Saltcake Dissolution''. The tests performed on saltcake from tank TX-113 were similar in scope to those completed in previous years on waste from tanks BY-102, BY-106, B-106, A-101, and S-102 (Herting 1998, 1999). In addition to the ''standard'' dissolution tests, new types of tests were performed this year related to feed stability and radionuclide distribution. The River Protection Project (RPP) is tasked with retrieving waste from double-shell and single-shell tanks to provide feed for vitrification. The RPP organization needs chemical and physical data to evaluate technologies for retrieving the waste. Little significant laboratory testing has been done to evaluate in-tank dissolution parameters for the various types of saltcake wastes that exist in single-shell tanks. A computer modeling program known as the Environmental Simulation Program (ESP), produced by OLI Systems, Inc of Morris Plains, New Jersey, is being used by the RPP organization to predict solubilities during dilution and retrieval of all tank waste types. Data from this task are provided to ESP users to support evaluation, refinement, and validation of the ESP model.

  17. Calcite dissolution in two deep eutrophic lakes

    SciTech Connect

    Ramisch, F.; Dittrich, M.; Mattenberger, C.; Wehrli, B.; Wueest, A.

    1999-10-01

    The calcium cycle, in particular carbonate dissolution, was analyzed in two deep eutrophic lakes, Lago di Lugano (288 m maximum depth) and Sempachersee (87 m) located in Switzerland. A box model approach was used to calculate calcite dissolution in the water column and at the sediment-water interface based on various lake monitoring data such as sediment traps, sediment cores, water and pore-water interface based on various lake monitoring data such as sediment traps, sediment cores, water and pore-water analysis. A model for stationary conditions allowing the calculation of calcite dissolution in the water column for a given particle size distribution was developed. The relative values of the simulated flux were consistent with sediment trap observations. The best fit of the dissolution rate constant of sinking calcite in Lago di Lugano was on the same order of magnitude (3 {center{underscore}dot} 10{sup {minus}10} kg{sup 1/3} s{sup {minus}1}) as published laboratory values for this surface controlled process. Both lakes show a similar specific calcite precipitation rate of 170 g Ca m{sup {minus}2} a{sup {minus}1}. The diffusive flux across the sediment-water interface amounts to about 15 and 10% of total calcite precipitation in Sempachersee and Lago di Lugano, respectively. However, 61% of the precipitated calcite is dissolved in the water column of Lago di Lugano compared to only 13% in Sempachersee. These results point towards the importance of grain size distributions and settling times in stratified deep waters as the two most important factors determining calcite retention in sediments of hard water lakes.

  18. Growth and dissolution kinetics of tetragonal lysozyme

    NASA Technical Reports Server (NTRS)

    Monaco, L. A.; Rosenberger, F.

    1993-01-01

    The growth and dissolution kinetics of lysozyme in a 25 ml solution bridge inside a closed growth cell was investigated. It was found that, under all growth conditions, the growth habit forming (110) and (101) faces grew through layer spreading with different growth rate dependence on supersaturation/temperature. On the other hand, (100) faces which formed only at low temperatures underwent a thermal roughening transition around 12 C.

  19. DISSOLUTION OF ZIRCONIUM AND ALLOYS THEREFOR

    DOEpatents

    Swanson, J.L.

    1961-07-11

    The dissolution of zirconium cladding in a water solution of ammonium fluoride and ammonium nitrate is described. The method finds particular utility in processing spent fuel elements for nuclear reactors. The zirconium cladding is first dissolved in a water solution of ammonium fluoride and ammonium nitrate; insoluble uranium and plutonium fiuorides formed by attack of the solvent on the fuel materiai of the fuel element are then separated from the solution, and the fuel materiai is dissolved in another solution.

  20. The chlorinated AHR ligand 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) promotes reactive oxygen species (ROS) production during embryonic development in the killifish (Fundulus heteroclitus)

    USGS Publications Warehouse

    Arzuaga, Xabier; Wassenberg, Deena; Giulio, Richard D.; Elskus, Adria

    2006-01-01

    Exposure to dioxin-like chemicals that activate the aryl hydrocarbon receptor (AHR) can result in increased cellular and tissue production of reactive oxygen species (ROS). Little is known of these effects during early fish development. We used the fish model, Fundulus heteroclitus, to determine if the AHR ligand and pro-oxidant 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) can increase ROS production during killifish development, and to test a novel method for measuring ROS non-invasively in a living organism. The superoxide-sensitive fluorescent dye, dihydroethidium (DHE), was used to detect in ovo ROS production microscopically in developing killifish exposed to PCB126 or vehicle. Both in ovo CYP1A activity (ethoxyresorufin-o-deethylase, EROD) and in ovo ROS were induced by PCB126. In ovo CYP1A activity was inducible by PCB126 concentrations as low as 0.003 nM, with maximal induction occurring at 0.3 nM PCB126. These PCB126 concentrations also significantly increased in ovo ROS production in embryonic liver, ROS being detectable as early as 5 days post-fertilization. These data demonstrate that the pro-oxidant and CYP1A inducer, PCB126, increases both CYP1A activity and ROS production in developing killifish embryos. The superoxide detection assay (SoDA) described in this paper provides a semi-quantitative, easily measured, early indicator of altered ROS production that can be used in conjunction with simultaneous in ovo measurements of CYP1A activity and embryo development to explore functional relationships among biochemical, physiological and developmental responses to AHR ligands.

  1. Dissolution of ordered precipitates under ion irradiation

    SciTech Connect

    Camus, E.; Bourdeau, F.; Abromeit, C.; Wanderka, N.; Wollenberger, H.

    1995-09-01

    The stability of the ordered {gamma}{prime} precipitates under 300-keV Ni{sup +} irradiation was investigated between room temperature and 623 K. The two competing mechanisms of destabilization by cascade producing irradiation, i.e. disordering and dissolution of the {gamma}{prime} precipitates in Nimonic PE16 alloy, has been studied separately by electron microscopy and field-ion microscopy with atom probe. At high temperatures, the precipitates are stable. At intermediate temperatures, the precipitates dissolve by ballistic mixing into the matrix, but the interface is restored by the radiation-enhanced atomic jumps. The order in the precipitates remains stable. At low temperatures, the precipitates are dissolved by atomic mixing. The dissolution proceeds in a diffusional manner with a diffusion coefficient normalized by the displacement rate D/K = 0.75 nm{sup 2}dpa{sup {minus}1}. The precipitates become disordered by a fluence of 0.1 dpa, whereas precipitate dissolution needs much higher fluences.

  2. Coamorphous repaglinide-saccharin with enhanced dissolution.

    PubMed

    Gao, Yuan; Liao, Jiao; Qi, Xuan; Zhang, Jianjun

    2013-06-25

    Recently, coamorphous systems composed of two drugs or a drug and a small molecule excipient, gained interests due to their ability in overcoming limitations associated with solid dispersions. In this study, coamorphous form of repaglinide (REP), a BCS class II anti-diabetic drug with low aqueous solubility and high permeability was achieved with saccharin (SAC) by solution crystallization and characterized. An accurate and precise HPLC method was established for the simultaneous determination of REP and SAC. Coamorphous REP-SAC with 1:1 stoichiometry had unique thermal behavior, obvious FTIR shifts and the absence of sharp diffraction peak, suggesting the formation of a coamorphous material and interaction of REP with SAC through hydrogen bonds formed between REP's secondary amine and SAC's carbonyl group. Coamorphous REP-SAC showed great improvement in solubility and dissolution under sink conditions in various media. In addition, it was conformed in supersaturated dissolution of coamorphous REP-SAC in distilled water that the coamorphous material had remarkably longer time length for REP to be remained at a supersaturated concentration and had better metastable solubility. This coamorphous system provides a feasible way to process drugs with low solubility into substances with enhanced dissolution and stabilized amorphous state that could be conducive to greater bioavailability than the crystalline drug.

  3. Perchloric acid dissolution of graphite and pyrolytic carbon.

    PubMed

    Buzzelli, G; Mosen, A W

    1977-06-01

    Three procedures are described for the wet oxidation, with perchloric acid, of nuclear graphite, pyrocarbon-coated fuel particles, and other carbonaceous materials used in high-temperature gas-cooled nuclear reactors (HTGRs). The first procedure is for dissolution of graphite and pyrolytic carbon, the second for dissolution of milligram quantities of HTGR fuel particles, and the last for dissolution of more easily oxidized carbonaceous materials such as charcoal. These procedures were developed primarily for the dissolution of irradiated materials before fission-product or burn-up analyses, but they are also used for dissolution of unirradiated materials.

  4. The effect of pH, grain size, and organic ligands on biotite weathering rates

    NASA Astrophysics Data System (ADS)

    Bray, Andrew W.; Oelkers, Eric H.; Bonneville, Steeve; Wolff-Boenisch, Domenik; Potts, Nicola J.; Fones, Gary; Benning, Liane G.

    2015-09-01

    Biotite dissolution rates were determined at 25 °C, at pH 2-6, and as a function of mineral composition, grain size, and aqueous organic ligand concentration. Rates were measured using both open- and closed-system reactors in fluids of constant ionic strength. Element release was non-stoichiometric and followed the general trend of Fe, Mg > Al > Si. Biotite surface area normalised dissolution rates (ri) in the acidic range, generated from Si release, are consistent with the empirical rate law:

  5. Assessing the Influence of Calcium Fluoride on Pyrite Electrochemical Dissolution and Mine Drainage pH.

    PubMed

    Wang, Luying; Liu, Qingyou; Zheng, Kai; Li, Heping

    2016-07-01

    We investigated the influence of dissolved calcium fluoride, CaF(aq), on the electrochemical dissolution of pyrite and the corresponding environmental effects on acid mine drainage (AMD). The experimental results showed that CaF(aq) promotes pyrite electrochemical dissolution. When the CaF(aq) concentration increased from 0 to 10 mg L up to saturation, the promoting efficiency was 15.80 and 57.25%, respectively. The reason for this phenomenon is that F and Fe form FeF, and at a higher scan potential, F and Fe form the ion complex FeF. The mechanisms include: (i) the decreasing charge transfer resistance at the double layer due to the iron fluorine complex formation; and (ii) the decreasing passivation resistance at the cover layer due to the strong penetration of F ions through it into the double layer. Although the hydrolysis reaction of F in solution could increase the pH value of mine drainage, the AMD was significantly aggravated because CaF(aq) promoted the pyrite electrochemical dissolution. PMID:27380083

  6. Theoretical Analysis of Drug Dissolution: I. Solubility and Intrinsic Dissolution Rate.

    PubMed

    Shekunov, Boris; Montgomery, Eda Ross

    2016-09-01

    The first-principles approach presented in this work combines surface kinetics and convective diffusion modeling applied to compounds with pH-dependent solubility and in different dissolution media. This analysis is based on experimental data available for approximately 100 compounds of pharmaceutical interest. Overall, there is a linear relationship between the drug solubility and intrinsic dissolution rate expressed through the total kinetic coefficient of dissolution and dimensionless numbers defining the mass transfer regime. The contribution of surface kinetics appears to be significant constituting on average ∼20% resistance to the dissolution flux in the compendial rotating disk apparatus at 100 rpm. The surface kinetics contribution becomes more dominant under conditions of fast laminar or turbulent flows or in cases when the surface kinetic coefficient may decrease as a function of solution composition or pH. Limitations of the well-known convective diffusion equation for rotating disk by Levich are examined using direct computational modeling with simultaneous dissociation and acid-base reactions in which intrinsic dissolution rate is strongly dependent on pH profile and solution ionic strength. It is shown that concept of diffusion boundary layer does not strictly apply for reacting/interacting species and that thin-film diffusion models cannot be used quantitatively in general case. PMID:26906172

  7. Dissociation of Multisubunit Protein-Ligand Complexes in the Gas Phase. Evidence for Ligand Migration

    NASA Astrophysics Data System (ADS)

    Zhang, Yixuan; Deng, Lu; Kitova, Elena N.; Klassen, John S.

    2013-10-01

    The results of collision-induced dissociation (CID) experiments performed on gaseous protonated and deprotonated ions of complexes of cholera toxin B subunit homopentamer (CTB5) with the pentasaccharide (β-D-Gal p-(1→3)-β-D-Gal pNAc-(1→4)[α-D-Neu5Ac-(2→3)]-β-D-Gal p-(1→4)-β-D-Glc p (GM1)) and corresponding glycosphingolipid (β-D-Gal p-(1→3)-β-D-Gal pNAc-(1→4)[α-D-Neu5Ac-(2→3)]-β-D-Gal p-(1→4)-β-D-Glc p-Cer (GM1-Cer)) ligands, and the homotetramer streptavidin (S4) with biotin (B) and 1,2-dipalmitoyl- sn-glycero-3-phosphoethanolamine-N-(biotinyl) (Btl), are reported. The protonated (CTB5 + 5GM1)n+ ions dissociated predominantly by the loss of a single subunit, with the concomitant migration of ligand to another subunit. The simultaneous loss of ligand and subunit was observed as a minor pathway. In contrast, the deprotonated (CTB5 + 5GM1)n- ions dissociated preferentially by the loss of deprotonated ligand; the loss of ligand-bound and ligand-free subunit were minor pathways. The presence of ceramide (Cer) promoted ligand migration and the loss of subunit. The main dissociation pathway for the protonated and deprotonated (S4 + 4B)n+/- ions, as well as for deprotonated (S4 + 4Btl)n- ions, was loss of the ligand. However, subunit loss from the (S4 + 4B)n+ ions was observed as a minor pathway. The (S4 + 4Btl)n+ ions dissociated predominantly by the loss of free and ligand-bound subunit. The charge state of the complex and the collision energy were found to have little effect on the relative contribution of the different dissociation channels. Thermally-driven ligand migration between subunits was captured in the results of molecular dynamics simulations performed on protonated (CTB5 + 5GM1)15+ ions (with a range of charge configurations) at 800 K. Notably, the migration pathway was found to be highly dependent on the charge configuration of the ion. The main conclusion of this study is that the dissociation pathways of multisubunit protein-ligand

  8. The impact of changing surface ocean conditions on the dissolution of aerosol iron

    NASA Astrophysics Data System (ADS)

    Fishwick, Matthew P.; Sedwick, Peter N.; Lohan, Maeve C.; Worsfold, Paul J.; Buck, Kristen N.; Church, Thomas M.; Ussher, Simon J.

    2014-11-01

    The proportion of aerosol iron (Fe) that dissolves in seawater varies greatly and is dependent on aerosol composition and the physicochemical conditions of seawater, which may change depending on location or be altered by global environmental change. Aerosol and surface seawater samples were collected in the Sargasso Sea and used to investigate the impact of these changing conditions on aerosol Fe dissolution in seawater. Our data show that seawater temperature, pH, and oxygen concentration, within the range of current and projected future values, had no significant effect on the dissolution of aerosol Fe. However, the source and composition of aerosols had the most significant effect on the aerosol Fe solubility, with the most anthropogenically influenced samples having the highest fractional solubility (up to 3.2%). The impact of ocean warming and acidification on aerosol Fe dissolution is therefore unlikely to be as important as changes in land usage and fossil fuel combustion. Our experimental results also reveal important changes in the size distribution of soluble aerosol Fe in solution, depending on the chemical conditions of seawater. Under typical conditions, the majority (77-100%) of Fe released from aerosols into ambient seawater existed in the colloidal (0.02-0.4 µm) size fraction. However, in the presence of a sufficient concentration of strong Fe-binding organic ligands (10 nM) most of the aerosol-derived colloidal Fe was converted to soluble Fe (<0.02 µm). This finding highlights the potential importance of organic ligands in retaining aerosol Fe in a biologically available form in the surface ocean.

  9. Mineral dissolution kinetics at the pore scale

    SciTech Connect

    Li, L.; Steefel, C.I.; Yang, L.

    2007-05-24

    Mineral dissolution rates in the field have been reported to be orders of magnitude slower than those measured in the laboratory, an unresolved discrepancy that severely limits our ability to develop scientifically defensible predictive or even interpretive models for many geochemical processes in the earth and environmental sciences. One suggestion links this discrepancy to the role of physical and chemical heterogeneities typically found in subsurface soils and aquifers in producing scale-dependent rates where concentration gradients develop. In this paper, we examine the possibility that scale-dependent mineral dissolution rates can develop even at the single pore and fracture scale, the smallest and most fundamental building block of porous media. To do so, we develop two models to analyze mineral dissolution kinetics at the single pore scale: (1) a Poiseuille Flow model that applies laboratory-measured dissolution kinetics at the pore or fracture wall and couples this to a rigorous treatment of both advective and diffusive transport, and (2) a Well-Mixed Reactor model that assumes complete mixing within the pore, while maintaining the same reactive surface area, average flow rate, and geometry as the Poiseuille Flow model. For a fracture, a 1D Plug Flow Reactor model is considered in addition to quantify the effects of longitudinal versus transverse mixing. The comparison of averaged dissolution rates under various conditions of flow, pore size, and fracture length from the three models is used as a means to quantify the extent to which concentration gradients at the single pore and fracture scale can develop and render rates scale-dependent. Three important minerals that dissolve at widely different rates, calcite, plagioclase, and iron hydroxide, are considered. The modeling indicates that rate discrepancies arise primarily where concentration gradients develop due to comparable rates of reaction and advective transport, and incomplete mixing via molecular

  10. Peridotite dissolution and carbonation rates at fracture surfaces under conditions relevant for in situ mineralization of CO2

    NASA Astrophysics Data System (ADS)

    van Noort, R.; Spiers, C. J.; Drury, M. R.; Kandianis, M. T.

    2013-04-01

    Whereas the dissolution of pure single phases (e.g. olivine and other mafic minerals) has been the focus of many studies, no investigation has been reported on the progress of reactions at and within polymineralic, transgranular fracture surfaces cutting peridotites. We document experiments that address the evolution of dissolving peridotite surfaces, and the rates of dissolution and carbonation reactions that occur at these surfaces, under both open- and closed-system conditions relevant for in situ CO2-sequestration. The results of experiments, conducted under quasi-open system conditions, on solid samples of peridotite whose surfaces were taken as an analogue of free fracture surfaces, demonstrate apparent rates of olivine dissolution at the free surfaces that are equivalent to or upwards of 100 times greater than those determined for pure olivine under similar conditions. This increase in apparent olivine dissolution rate is ascribed to fluid penetration along grain boundaries and veins, which resulted in increased accessibility of reactive olivine surface area. Apparent dissolution rates under closed system conditions, where serial olivine dissolution and magnesite precipitation take place, are ˜1 order of magnitude slower owing to changes in fluid composition and pH. In both of these reaction environments, it is apparent that serpentinized veins and mineral grain boundaries within the peridotite allowed fluids to penetrate the rock and to promote the release of divalent metals and silica from within the sample or simulated fracture walls. These results indicate that the microstructure of free (fracture) surfaces exerts a dominant control on peridotite dissolution and carbonation rates, relative to the proportion of highly reactive minerals that compose such ultramafic rock. The rapid dissolution we observe under open system conditions implies that CO2-mineralization may be viable, in open systems, if the composition of injected fluids can be maintained at or

  11. Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene

    SciTech Connect

    Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo; Aykol, Muratahan; Luo, Langli; Wu, Jinsong; Myers, Benjamin D.; Iddir, Hakim; Russell, John T.; Saldana, Spencer J.; Kumar, Rajan; Thackeray, Michael M.; Curtiss, Larry A.; Dravid, Vinayak P.; Wolverton, Christopher M.; Hersam, Mark C.

    2015-06-24

    Spinel-structured LiMn 2 O 4 (LMO) is a desirable cathode material for Li-ion batteries due to its low cost, abundance, and high power capability. However, LMO suffers from limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, it is shown that single-layer graphene coatings suppress manganese dissolution, thus enhancing the performance and lifetime of LMO cathodes. Relative to lithium cells with uncoated LMO cathodes, cells with graphene-coated LMO cathodes provide improved capacity retention with enhanced cycling stability. X-ray photoelectron spectroscopy reveals that graphene coatings inhibit manganese depletion from the LMO surface. Additionally, transmission electron microscopy demonstrates that a stable solid electrolyte interphase is formed on graphene, which screens the LMO from direct contact with the electrolyte. Density functional theory calculations provide two mechanisms for the role of graphene in the suppression of manganese dissolution. First, common defects in single-layer graphene are found to allow the transport of lithium while concurrently acting as barriers for manganese diffusion. Second, graphene can chemically interact with Mn 3+ at the LMO electrode surface, promoting an oxidation state change to Mn 4+ , which suppresses dissolution.

  12. Effects of pH and phosphate on CeO2 nanoparticle dissolution.

    PubMed

    Dahle, Jessica T; Livi, Ken; Arai, Yuji

    2015-01-01

    As the result of rapidly grown nanotechnology industries, release of engineered nanoparticles (ENPs) to environment has increased, posing in a serious risk to environmental and human health. To better understand the chemical fate of ENPs in aquatic environments, solubility of CeO2 NPs was investigated using batch dissolution experiments as a function of pH (1.65-12.5), [phosphate] and particle size (33 and 78 nm). It was found that CeO2 dissolution was only significant at pH<5 and inversely proportional to surface area. After 120 h, the release of Ce was ∼3 times greater in large NPs than that in small NPs that is likely contributed by the difference in exchangeable Ce(III) impurity (small: 0.3 mM kg(-1), large: 1.56 mM kg(-1)). When 100 μM of phosphate was added, the dissolution rate of CeO2 NPs was decreased in small NPs by 15% at pH 1.65 and 75% at pH 4.5 and in large NPs by 56% at pH 1.65 and 63% at pH 4.5. The inner-sphere surface complexation of P that is revealed by the zeta potential measurements is effectively suppressing the CeO2 NP dissolution. Predicting the fate and transport of CeO2 NPs in aquatic environment, pH and P ligands might play important roles in controlling the solubility of CeO2 NPs.

  13. Role of root exudates in dissolution of Cd containing iron oxides

    NASA Astrophysics Data System (ADS)

    Rosenfeld, C.; Martinez, C. E.

    2011-12-01

    Dissolved organic matter (DOM) in the rhizosphere contains organic acids, amino acids and more complex organic molecules that can substantially impact the solubility of soil solid phases. Plant roots and soil microorganisms contribute a large fraction of these organic compounds to DOM, potentially accelerating the transfer of solid phase elements into solution. In highly contaminated soils, heavy metals such as Cd are commonly found coprecipitated with common minerals (e.g. iron oxides). Introducing or changing vegetation on these contaminated soils may increase DOM levels in the soil pore fluids and thus enhance the biological and chemical weathering of soil minerals. Here, we investigate the role of root exudates on mineral dissolution and Cd mobility in contaminated soils. We hypothesize that plant exudates containing nitrogen and sulfur functional groups will dissolve Cd-containing mineral phases to a greater extent than exudates containing only oxygen functional groups, resulting in higher Cd concentrations in solution. Two different iron oxide mineral phases were utilized in a laboratory-scale model study system investigating the effects of low molecular weight, oxygen-, nitrogen-, and sulfur-containing organic compounds on mineral dissolution. Goethite (α-FeOOH) was synthesized in the laboratory with 0, 2.4, 5, and 100 theoretical mol% Cd, and franklinite (ZnFe2O4) was prepared with 0, 10, and 25 theoretical mol% Cd. Phase identity of all minerals was verified with X-ray diffraction (XRD). All minerals were reacted with 0.01 mM solutions containing one of four different organic ligands (oxalic acid, citric acid, histidine or cysteine) and aliquots of these solutions were sampled periodically over 40 days. Results from solution samples suggest that oxalic acid, citric acid, and histidine consistently increase mineral dissolution relative to the control (no organic compound present) while cysteine consistently inhibits dissolution relative to the control in

  14. The combined effect of temperature and pH on albite dissolution rate under far-from-equilibrium conditions

    NASA Astrophysics Data System (ADS)

    Gruber, Chen; Kutuzov, Ilya; Ganor, Jiwchar

    2016-08-01

    Two of the most studied aspects of albite dissolution kinetics are the effects of temperature and pH. Previous studies quantified the effect of pH on albite dissolution rate under constant temperature. These studies suggested that the effect of pH on dissolution rate can be attributed to three independent dissolution mechanisms that are dominant in different pH region: acidic - proton-promoted, neutral - water-promoted and alkaline - hydroxide-promoted. Based on experimental results, those studies developed a rate law to predict albite dissolution rate as a function of pH, assuming that the effect of pH is temperature independent. The effect of temperature was attributed either to the temperature dependency of the rate under constant pH or that of the rate law coefficients. Nevertheless no unified rate law that combines both effects was suggested. When applying the effects of temperature and pH assuming they are independent of each other in order to predict the dissolution rate at pH of about 5 and various temperatures, the predicted rate overestimate the rate by 0.5-1 order of magnitude. The current study develops and suggests the use of new rate law that is based on two fast adsorption reactions of protons and hydroxides on two different surface sites. The new rate law considers the effect of surface coverage of protons and hydroxides that is temperature dependent. The new rate law successfully describes the variation of albite dissolution rate (about 8 orders of magnitude) under wide temperature (3.6-300 °C) and pH (1.20-12.40) ranges. Under slightly acidic conditions (pH 5-7) the new rate law predicts a minimum rate zone that was not observed before. In order to confirm whether this minimum rate zone does exist, three SPBE (single-point-batch-experiment) of albite dissolution were conducted at pH 5 and temperatures of 3.6, 25 and 50 °C. The SPBE experiments confirm the existence of minimum rate zone predicted by the independent new rate law. The new rate law

  15. Systematic review of forsterite dissolution rate data

    NASA Astrophysics Data System (ADS)

    Rimstidt, J. Donald; Brantley, Susan L.; Olsen, Amanda A.

    2012-12-01

    This paper demonstrates a method for systematic analysis of published mineral dissolution rate data using forsterite dissolution as an example. The steps of the method are: (1) identify the data sources, (2) select the data, (3) tabulate the data, (4) analyze the data to produce a model, and (5) report the results. This method allows for a combination of critical selection of data, based on expert knowledge of theoretical expectations and experimental pitfalls, and meta-analysis of the data using statistical methods. Application of this method to all currently available forsterite dissolution rates (0 < pH < 14, and 0 < T < 150 °C) normalized to geometric surface area produced the following rate equations: For pH < 5.6 and 0° < T < 150 °C, based on 519 data logr=6.05(0.22)-0.46(0.02)pH-3683.0(63.6)1/T(R2=0.88) For pH > 5.6 and 0° < T < 150 °C, based on 125 data logr=4.07(0.38)-0.256(0.023)pH-3465(139)1/T(R2=0.92) The R2 values show that ˜10% of the variance in r is not explained by variation in 1/T and pH. Although the experimental error for rate measurements should be ± ˜30%, the observed error associated with the log r values is ˜0.5 log units (±300% relative error). The unexplained variance and the large error associated with the reported rates likely arises from the assumption that the rates are directly proportional to the mineral surface area (geometric or BET) when the rate is actually controlled by the concentration and relative reactivity of surface sites, which may be a function of duration of reaction. Related to these surface area terms are other likely sources of error that include composition and preparation of mineral starting material. Similar rate equations were produced from BET surface area normalized rates. Comparison of rate models based on geometric and BET normalized rates offers no support for choosing one normalization method over the other. However, practical considerations support the use of geometric surface area normalization

  16. Dissolution of wood in ionic liquids.

    PubMed

    Kilpeläinen, Ilkka; Xie, Haibo; King, Alistair; Granstrom, Mari; Heikkinen, Sami; Argyropoulos, Dimitris S

    2007-10-31

    The present paper demonstrates that both hardwoods and softwoods are readily soluble in various imidazolium-based ionic liquids (ILs) under gentle conditions. More specifically, a variety of ionic liquids can only partially dissolve wood chips, whereas ionic liquids such as 1-butyl-3-methylimidazolium chloride and 1-allyl-3-methylimidazolium chloride have good solvating power for Norway spruce sawdust and Norway spruce and Southern pine thermomechanical pulp (TMP) fibers. Despite the fact that the obtained solutions were not fully clear, these ionic liquids provided solutions which permitted the complete acetylation of the wood. Alternatively, transparent amber solutions of wood could be obtained when the dissolution of the same lignocellulosic samples was attempted in 1-benzyl-3-methylimidazolium chloride. This realization was based on a designed augmented interaction of the aromatic character of the cation of the ionic liquid with the lignin in the wood. After dissolution, wood can be regenerated as an amorphous mixture of its original components. The cellulose of the regenerated wood can be efficiently digested to glucose by a cellulase enzymatic hydrolysis treatment. Furthermore, completely acetylated wood was found to be readily soluble in chloroform, allowing, for the first time, detailed proton nuclear magnetic resonance (NMR) spectra and NMR diffusion measurements to be made. It was thus demonstrated that the dissolution of wood in ionic liquids now offers a variety of new possibilities for its structural and macromolecular characterization, without the prior isolation of its individual components. Furthermore, considering the relatively wide solubility and compatibility of ionic liquids with many organic or inorganic functional chemicals or polymers, it is envisaged that this research could create a variety of new strategies for converting abundant woody biomass to valuable biofuels, chemicals, and novel functional composite biomaterials.

  17. Saltcake Dissolution FY 2002 Status Report

    SciTech Connect

    HERTING, D.L.

    2002-09-26

    Laboratory tests were completed on the dissolution characteristics of Hanford saltcake waste from single-shell waste tanks 241-B-109 and 241-SX-101 (henceforth referred to as B-109 and SX-101). The River Protection Project (RPP) is tasked with retrieving waste from double-shell and single-shell tanks to provide feed for vitrification. The RPP organization needs chemical and physical data to evaluate technologies for retrieving the waste. Little relevant laboratory testing has been done to evaluate in-tank dissolution parameters for the various types of saltcake wastes that exist in single-shell tanks. A computer modeling program known as the Environmental Simulation Program (ESP), produced by OLI Systems, Inc. of Morris Plains, New Jersey, is being used by the RPP organization to predict solubilities during dilution and retrieval of all tank waste types. Data from this task are provided to ESP users to support evaluation, refinement, and validation of the ESP model. Cascade (or ''stepwise'') dissolution tests were performed on composite saltcake samples from both tanks. The purpose of these tests is to evaluate the solid/liquid phase distribution of chemicals and radionuclides during tank waste retrieval operations. Solid phase identification tests were also performed on saltcake from both tanks. Weight percent (wt%) dilution is defined in this report as 100 times the weight of diluent (water or 2 M NaOH solution) divided by the weight of undiluted saltcake composite sample. A 50% dilution, for example, would be 50 g of H{sub 2}O (or 50 g of 2 M NaOH) added to 100 g of undiluted composite sample. Volume percent (Vol%) dilution is defined as 100 times the volume of diluent divided by the calculated volume of undiluted sample. Weight percent dilutions are measured directly by weighing the undiluted sample and diluent. Volume percent dilutions are estimated from the known volume of diluent and calculated volume of undiluted sample.

  18. LigandRNA: computational predictor of RNA-ligand interactions.

    PubMed

    Philips, Anna; Milanowska, Kaja; Lach, Grzegorz; Bujnicki, Janusz M

    2013-12-01

    RNA molecules have recently become attractive as potential drug targets due to the increased awareness of their importance in key biological processes. The increase of the number of experimentally determined RNA 3D structures enabled structure-based searches for small molecules that can specifically bind to defined sites in RNA molecules, thereby blocking or otherwise modulating their function. However, as of yet, computational methods for structure-based docking of small molecule ligands to RNA molecules are not as well established as analogous methods for protein-ligand docking. This motivated us to create LigandRNA, a scoring function for the prediction of RNA-small molecule interactions. Our method employs a grid-based algorithm and a knowledge-based potential derived from ligand-binding sites in the experimentally solved RNA-ligand complexes. As an input, LigandRNA takes an RNA receptor file and a file with ligand poses. As an output, it returns a ranking of the poses according to their score. The predictive power of LigandRNA favorably compares to five other publicly available methods. We found that the combination of LigandRNA and Dock6 into a "meta-predictor" leads to further improvement in the identification of near-native ligand poses. The LigandRNA program is available free of charge as a web server at http://ligandrna.genesilico.pl.

  19. New mixing system in dissolution isoperibol microcalorimeter

    NASA Astrophysics Data System (ADS)

    Moreno-Piraján, Juan Carlos; Giraldo-Gutierréz, Liliana

    2007-04-01

    In order to determine dissolution enthalpies of small amounts of easily or slightly soluble solids, a new cell for batch isoperibolic microcalorimetry was developed at the Universities of the Andes and the National of Colombia. An innovative mixing system for avoiding error due to the common effect of the brittle point breakage has been designed for this cell. The cell has a capacity of 40ml and the sample holder can bear solid samples between 10.0 and 30.0mg. The high stability of the base line allows solution experiments to be extended over several hours. All measurements reported were conducted at 298.15K using water as solvent.

  20. New mixing system in dissolution isoperibol microcalorimeter.

    PubMed

    Moreno-Piraján, Juan Carlos; Giraldo-Gutierréz, Liliana

    2007-04-01

    In order to determine dissolution enthalpies of small amounts of easily or slightly soluble solids, a new cell for batch isoperibolic microcalorimetry was developed at the Universities of the Andes and the National of Colombia. An innovative mixing system for avoiding error due to the common effect of the brittle point breakage has been designed for this cell. The cell has a capacity of 40 ml and the sample holder can bear solid samples between 10.0 and 30.0 mg. The high stability of the base line allows solution experiments to be extended over several hours. All measurements reported were conducted at 298.15 K using water as solvent.

  1. Match quality, new information, and marital dissolution.

    PubMed

    Weiss, Y; Willis, R J

    1997-01-01

    "This article investigates the role of surprises in marital dissolution [in the United States]. Surprises consists of changes in the predicted earning capacity of either spouse. Data from the National Longitudinal Study of the High School Class of 1972 is used. We find that an unexpected increase in the husband's earning capacity reduces the divorce hazard, while an unexpected increase in the wife's earning capacity raises the divorce hazard. Couples sort into marriage according to characteristics that are likely to enhance the stability of the marriage. The divorce hazard is initially increasing with the duration of marriage, and the presence of children and high levels of property stabilizes the marriage."

  2. Analysis of macromolecules, ligands and macromolecule-ligand complexes

    DOEpatents

    Von Dreele, Robert B.

    2008-12-23

    A method for determining atomic level structures of macromolecule-ligand complexes through high-resolution powder diffraction analysis and a method for providing suitable microcrystalline powder for diffraction analysis are provided. In one embodiment, powder diffraction data is collected from samples of polycrystalline macromolecule and macromolecule-ligand complex and the refined structure of the macromolecule is used as an approximate model for a combined Rietveld and stereochemical restraint refinement of the macromolecule-ligand complex. A difference Fourier map is calculated and the ligand position and points of interaction between the atoms of the macromolecule and the atoms of the ligand can be deduced and visualized. A suitable polycrystalline sample of macromolecule-ligand complex can be produced by physically agitating a mixture of lyophilized macromolecule, ligand and a solvent.

  3. Carbodiphosphoranes and Related Ligands

    NASA Astrophysics Data System (ADS)

    Petz, Wolfgang; Frenking, Gernot

    The theoretical and experimental research on carbodiphosphoranes C(PR3)2 and related compounds CL2, both as free molecules and as ligands in transition metal complexes, is reviewed. Carbodiphosphoranes are examples of divalent carbon(0) compounds CL2 which have peculiar donor properties that are due to the fact that the central carbon atom has two lone electron pairs. The bonding situation is best described in terms of L→C←L donor acceptor interactions which distinguishes CL2 compounds (carbones) from divalent carbon(II) compounds (carbenes) through the number of lone electron pairs. The structures and stabilities of transition metal complexes with ligands CL2 can be understood and predictions can be made considering the double donor ability of the carbone compounds.

  4. Ligand exclusion on acetylcholinesterase.

    PubMed

    Berman, H A; Leonard, K

    1990-11-27

    This paper examines covalent reactivity of AchE with respect to cationic and uncharged methylphosphonates and substrates in the absence and presence of cationic ligands selective for the active center and the peripheral anionic site. The organophosphorus inhibitors are enantiomeric alkyl methylphosphonothioates (1-5) containing cycloheptyl and isopropyl phosphono ester groups and S-methyl, S-n-pentyl, and S-[beta-(trimethylammonio)ethyl] leaving groups; these agents differ in their configuration about phosphorus and their steric, hydrophobic, and electrostatic characteristics. The synthetic substrates examined are acetylthiocholine, p-nitrophenyl acetate, and 7-acetoxy-4-methylcoumarin (7AMC). Antagonism of the methylphosphonothioate reaction by cationic ligands is strongly dependent on the nature of both the cation and the methylphosphonate but independent of the configuration about phosphorus. While all cations cause linear mixed inhibition of acetylthiocholine hydrolysis, there are observed a variety of inhibition patterns of 7AMC and p-nitrophenyl acetate hydrolysis that are distinctly nonlinear, as well as patterns in which the reciprocal plots intersect in the upper right quadrant. Strong antagonism of cationic (methylphosphonyl)thiocholines correlates very well with linear inhibition of acetylthiocholine. Ligands that cause only negligible antagonism of the uncharged methylphosphonates display nonlinear inhibition of uncharged substrates. These relationships, since they are most pronounced for peripheral site ligands and are strongly dependent on the charge carried by the reactant, suggest that the peripheral anionic site alters enzyme reactivity through an electrostatic interaction with the net negative active center. Such behavior indicates a potential role for the peripheral anionic site in conserving AchE catalytic efficiency within a narrow range of values. PMID:2271673

  5. EGF receptor ligands: recent advances

    PubMed Central

    Singh, Bhuminder; Carpenter, Graham; Coffey, Robert J.

    2016-01-01

    Seven ligands bind to and activate the mammalian epidermal growth factor (EGF) receptor (EGFR/ERBB1/HER1): EGF, transforming growth factor-alpha (TGFA), heparin-binding EGF-like growth factor (HBEGF), betacellulin (BTC), amphiregulin (AREG), epiregulin (EREG), and epigen (EPGN). Of these, EGF, TGFA, HBEGF, and BTC are thought to be high-affinity ligands, whereas AREG, EREG, and EPGN constitute low-affinity ligands. This focused review is meant to highlight recent studies related to actions of the individual EGFR ligands, the interesting biology that has been uncovered, and relevant advances related to ligand interactions with the EGFR.

  6. EGF receptor ligands: recent advances.

    PubMed

    Singh, Bhuminder; Carpenter, Graham; Coffey, Robert J

    2016-01-01

    Seven ligands bind to and activate the mammalian epidermal growth factor (EGF) receptor (EGFR/ERBB1/HER1): EGF, transforming growth factor-alpha (TGFA), heparin-binding EGF-like growth factor (HBEGF), betacellulin (BTC), amphiregulin (AREG), epiregulin (EREG), and epigen (EPGN). Of these, EGF, TGFA, HBEGF, and BTC are thought to be high-affinity ligands, whereas AREG, EREG, and EPGN constitute low-affinity ligands. This focused review is meant to highlight recent studies related to actions of the individual EGFR ligands, the interesting biology that has been uncovered, and relevant advances related to ligand interactions with the EGFR. PMID:27635238

  7. EGF receptor ligands: recent advances

    PubMed Central

    Singh, Bhuminder; Carpenter, Graham; Coffey, Robert J.

    2016-01-01

    Seven ligands bind to and activate the mammalian epidermal growth factor (EGF) receptor (EGFR/ERBB1/HER1): EGF, transforming growth factor-alpha (TGFA), heparin-binding EGF-like growth factor (HBEGF), betacellulin (BTC), amphiregulin (AREG), epiregulin (EREG), and epigen (EPGN). Of these, EGF, TGFA, HBEGF, and BTC are thought to be high-affinity ligands, whereas AREG, EREG, and EPGN constitute low-affinity ligands. This focused review is meant to highlight recent studies related to actions of the individual EGFR ligands, the interesting biology that has been uncovered, and relevant advances related to ligand interactions with the EGFR. PMID:27635238

  8. Rescoring ligand docking poses.

    PubMed

    Zhong, Shijun; Zhang, Youping; Xiu, Zhilong

    2010-05-01

    The ranking of ligand docking poses according to certain scoring systems to identify the best fit is the most important step in virtual database screening for drug discovery. By focusing on method development strategy, this review provides possibilities for constructing rescoring approaches based on an overview of recent developments in the field. These developments can be classified into three categories. The first category involves a scaling approach that employs a factor to scale the primary scoring function. These scaling factors are defined with respect to the geometrical match between the location of a ligand and the target binding site, or defined according to a molecular weight distribution consistent with the empirical range of molecular weights of drug-like compounds. The second category involves consensus scoring approaches that use multiple scoring functions to rank the ligand poses retained in a docking procedure, based on the preliminary ranking according to a primary scoring function. The final category involves the addition of selected accuracy-oriented energy terms, such as the solvent effect and quantum mechanics/molecular mechanics treatments. PMID:20443166

  9. Dissolution of Uranium Oxides Under Alkaline Oxidizing Conditions

    SciTech Connect

    Smith, Steven C.; Peper, Shane M.; Douglas, Matthew; Ziegelgruber, Kate L.; Finn, Erin C.

    2009-11-01

    Bench scale experiments were conducted to determine the dissolution characteristics of uranium oxide powders (UO2, U3O8, and UO3) in aqueous peroxide-carbonate solutions. Experimental parameters included H2O2 concentration, carbonate counter cation (NH4+, Na+, K+, and Rb+), and pH. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M. The three uranium oxide powders exhibited different dissolution patterns however, UO3 exhibited prompt complete dissolution. Carbonate counter cation affected the dissolution kinetics. There is minimal impact of solution pH, over the range 8.8 to 10.6, on initial dissolution rate.

  10. Dissolution rate of griseofulvin in bile salt solutions.

    PubMed

    de Smidt, J H; Offringa, J C; Crommelin, D J

    1991-04-01

    Bile salts increase the apparent solubility of lipophilic poorly water-soluble drugs like griseofulvin. In this study, the dissolution kinetics of griseofulvin in solutions of bile salts (sodium taurocholate and sodium cholate) were investigated. A rotating disk apparatus was chosen to monitor dissolution kinetics; it well-defined hydrodynamic conditions allowed for analysis of the behavior of bile salt micelles under different conditions. Griseofulvin solubility and dissolution rate increased with increasing bile salt concentration in the dissolution medium. The enhancement of the dissolution rate was not linearly related to the solubility increase, as diffusional transport of the solubilized drug proved to be less efficient than transport of the unsolubilized ("free") drug. The dissolution process proved to be controlled by convective diffusion. An analysis of the data with the phase separation model provided results for the micellar diffusion coefficient comparable with literature data obtained with different techniques. PMID:1865343

  11. Dissolution of Platinum in the Operational Range of Fuel Cells

    PubMed Central

    Keeley, Gareth P.; Geiger, Simon; Zeradjanin, Aleksandar R.; Hodnik, Nejc; Kulyk, Nadiia

    2015-01-01

    Abstract One of the most important practical issues in low‐temperature fuel‐cell catalyst degradation is platinum dissolution. According to the literature, it initiates at 0.6–0.9 VRHE, whereas previous time‐ and potential‐resolved inductively coupled plasma mass spectrometry (ICP–MS) experiments, however, revealed dissolution onset at only 1.05 VRHE. In this manuscript, the apparent discrepancy is addressed by investigating bulk and nanoparticulated catalysts. It is shown that, given enough time for accumulation, traces of platinum can be detected at potentials as low as 0.85 VRHE. At these low potentials, anodic dissolution is the dominant process, whereas, at more positive potentials, more platinum dissolves during the oxide reduction after accumulation. Interestingly, the potential and time dissolution dependence is similar for both types of electrode. Dissolution processes are discussed with relevance to fuel‐cell operation and plausible dissolution mechanisms are considered. PMID:27525206

  12. Buffering children from marital conflict and dissolution.

    PubMed

    Katz, L F; Gottman, J M

    1997-06-01

    Examined several protective mechanisms that may reduce deleterious correlates of marital conflict and marital dissolution in young children. One set of potential buffers focused on parent-child interaction: parental warmth, parental scaffolding/praise, and inhibition of parental rejection. As a second set of potential buffers, each parent was interviewed about their "meta-emotion philosophy"--that is, their feelings about their own emotions, and their attitudes and responses to their children's anger and sadness. The third set of potential buffers concerned intraindividual characteristics of the child, including the child's intelligence and regulatory physiology (basal vagal tone and vagal suppression). Fifty-six families with a preschool child were studied at two time points: when the children were 5 years old (Time 1) and again when the children were 8 years old (Time 2). At Time 1, naturalistic observations of marital and parent-child interaction were conducted and assessment of child regulatory physiology was obtained through measures of basal vagal tone and suppression of vagal tone. Parents were also interviewed individually about their feelings about their own and their children's emotions, and children's intelligence was assessed. At Time 2, assessment of child outcomes were obtained, including observations of peer interaction, mother ratings of behavior problems and mother and teacher ratings of peer aggression, mother ratings of child physical illness, and measures of achievement. Results indicated that all Time 1 buffering factors protected children in face of marital conflict and dissolution. PMID:9169376

  13. Self potential observations during DNAPL dissolution

    NASA Astrophysics Data System (ADS)

    Ntarlagiannis, D.; Slater, L.; Kulessa, B.; Russell, C.; Kalin, R.; Ferguson, A.; Graber, J.

    2006-05-01

    Dense non aqueous phase liquids (DNAPLs) are a major environmental problem and are considered to be long term heavy contaminant sources in the subsurface. Accurate monitoring of DNAPL breakdown is required to monitor remediation efforts. We aim to evaluate the efficiency of geophysical methods to monitor DNAPL remediation. Toward this goal we performed self potential (SP) measurements on laboratory columns packed with DNAPL contaminated sand undergoing (a) biodegradation, and (b) abiotic DNAPL dissolution. Geochemical monitoring showed higher concentration of dissolved DNAPL byproducts in the abiotic columns; the use of HgCl2 as a biocide probably increased the rates of DNAPL dissolution in the abiotic columns. The concentration of DNAPL byproducts is significantly lower in the biotic columns due to microbial activity since DNAPL degrading bacteria within the column consume the breakdown products. SP responses are significantly higher (~ 90 mV) in the abiotic columns; in the microbial active columns SP values remain steady with a value ~ 10 mV. High SP signals (up to 110 mV) are associated with DNAPL byproduct concentration gradients within the abiotic columns and exhibit a temporal behavior that mimics total organic carbon concentrations. Although microbial activity in organic rich contaminated areas has been associated with strong negative SP anomalies our results show that positive SP anomalies can also be generated in contaminated areas in the absence of any microbial activity. We discuss a possible SP source mechanism and the implications in geophysical monitoring of DNAPL remedial processes.

  14. Buffering children from marital conflict and dissolution.

    PubMed

    Katz, L F; Gottman, J M

    1997-06-01

    Examined several protective mechanisms that may reduce deleterious correlates of marital conflict and marital dissolution in young children. One set of potential buffers focused on parent-child interaction: parental warmth, parental scaffolding/praise, and inhibition of parental rejection. As a second set of potential buffers, each parent was interviewed about their "meta-emotion philosophy"--that is, their feelings about their own emotions, and their attitudes and responses to their children's anger and sadness. The third set of potential buffers concerned intraindividual characteristics of the child, including the child's intelligence and regulatory physiology (basal vagal tone and vagal suppression). Fifty-six families with a preschool child were studied at two time points: when the children were 5 years old (Time 1) and again when the children were 8 years old (Time 2). At Time 1, naturalistic observations of marital and parent-child interaction were conducted and assessment of child regulatory physiology was obtained through measures of basal vagal tone and suppression of vagal tone. Parents were also interviewed individually about their feelings about their own and their children's emotions, and children's intelligence was assessed. At Time 2, assessment of child outcomes were obtained, including observations of peer interaction, mother ratings of behavior problems and mother and teacher ratings of peer aggression, mother ratings of child physical illness, and measures of achievement. Results indicated that all Time 1 buffering factors protected children in face of marital conflict and dissolution.

  15. Coupled Mineral Dissolution and Precipitation Reactions in Shale-Hydraulic Fracturing Fluid Systems

    NASA Astrophysics Data System (ADS)

    Joe-Wong, C. M.; Harrison, A. L.; Thomas, D.; Dustin, M. K.; Jew, A. D.; Brown, G. E.; Maher, K.; Bargar, J.

    2015-12-01

    Hydraulic fracturing of low-permeability, hydrocarbon-rich shales has recently become an important energy source in the United States. However, hydrocarbon recovery rates are low and drop rapidly after a few months. Hydraulic fracture fluids, which contain dissolved oxygen and numerous organic additives, induce dissolution and precipitation reactions that change the porosity and permeability of the shale. To investigate these reactions, we studied the interactions of four shales (Eagle Ford, Barnett, Marcellus, and Green River) with a simulated hydraulic fracture fluid in batch reactors at 80 °C. The shales were chosen for both economic viability and chemical variety, allowing us to explore the reactivities of different components. The Eagle Ford shale is carbonate rich, and the Green River shale contains significant siderite and kerogen. The Barnett shale also has a high organic content, while the Marcellus shale has the highest fractions of clay and pyrite. Our experiments show that hydrochloric acid in the fluid promotes carbonate mineral dissolution, rapidly raising the pH from acidic to circumneutral levels for the Eagle Ford and Green River shales. Dissolution textures in the Green River shale and large cavities in the Barnett shale indicate significant mineralogical and physical changes in the reacted rock. Morphological changes are not readily apparent in the Eagle Ford and Marcellus shales. For all shales, ongoing changes to the solution Al: Si ratio suggest incongruent aluminosilicate dissolution. Siderite or pyrite dissolution occurs within days and is followed by the formation of secondary Fe precipitates in suspension and coating the walls of the reactor. However, little evidence of any coatings on shale surfaces was found. The net effect of these reactions on porosity and permeability and their influence on the long-term efficacy of oil and gas recovery after hydraulic fracturing are critical to the energy landscape of the United States.

  16. The role of carboxylic acids in albite and quartz dissolution: An experimental study under diagenetic conditions

    SciTech Connect

    Franklin, S.P. ); Hajash, A. Jr.; Tieh, T.T. ); Dewers, T.A. )

    1994-10-01

    Simple water soluble organic acids may promote secondary porosity development in sandstones during diagenesis by increasing feldspar solubility and dissolution rate. To test this hypothesis, Amelia albite and Brazilian hydrothermal quartz were reacted with 0.07 m acetate and 0.07 m acetate-0.005 m oxalate solutions at selected pH values, and distilled water. Pore fluid chemistry was monitored through time at various flow rates to obtain both solubility and dissolution rate data. The experiments were conducted in large volume, semi-static, flow-through systems at 100[degrees]C and 347 bars. These systems simulate subsurface flow rates, low mass water/rock, and high surface area/fluid mass. Acetate and acetate + oxalate solutions significantly increase albite solubility at temperatures, pressures, and pH values typical of diagenetic environments. Albite solubilities increased in acetate and acetate + oxalate solutions by factors of 2 and 3.4, respectively, compared to distilled water. In these same solutions, Al concentrations were [approx] 140 and [approx] 480 times higher than that calculated for kaolinite solubility at the same conditions without organic species. These enhanced solubilities occur at pH values (4.6-4.8) that may overlap with formation waters. In contrast to albite, quartz solubility was essentially identical in all solutions investigated. Dissolution rates in the acid region decreased with increasing pH in the acetate and acetate + oxalate solutions. Slopes of log rate vs. pH curves were [approx] 0.6 for acetate and [approx] 0.3 for acetate + oxalate. Although the effects of acetate on the dissolution rate are small, the effects of oxalate are significant. A rate law valid for albite dissolution at 100[degrees]C, oxalate concentrations to 0.01 m, and pH values ranging from 3.4 to 5.5 is given.

  17. Quartz crystal microbalance thin-film dissolution rate monitor

    NASA Astrophysics Data System (ADS)

    Hinsberg, William D.; Kanazawa, Kay K.

    1989-03-01

    We describe the details of construction and operation of an instrument useful for the characterization of dissolution kinetics of thin films. This device, based on a quartz crystal microbalance operating in contact with a liquid, avoids the limitations associated with the use of optical, electrical, and mechanical dissolution rate measurement techniques. The QCM rate monitor has general application to the measurement of the kinetics of dissolution of transparent and opaque thin films such as dielectrics, metals, and polymeric resists.

  18. On the dissolution properties of GaAs in Ga

    NASA Technical Reports Server (NTRS)

    Davidson, M. C.; Moynahan, A. H.

    1977-01-01

    The dissolution of GaAs in Ga was studied to determine the nature and cause of faceting effects. Ga was allowed to dissolve single crystalline faces under isothermal conditions. Of the crystalline planes with low number indices, only the (100) surface showed a direct correlation of dissolution sites to dislocations. The type of dissolution experienced depended on temperature, and there were three distinct types of behavior.

  19. Dissolution of beryllium in artificial lung alveolar macrophage phagolysosomal fluid.

    PubMed

    Stefaniak, Aleksandr B; Virji, M Abbas; Day, Gregory A

    2011-05-01

    Dissolution of a lung burden of poorly soluble beryllium particles is hypothesized to be necessary for development of chronic beryllium lung disease (CBD) in humans. As such, particle dissolution rate must be sufficient to activate the lung immune response and dissolution lifetime sufficient to maintain chronic inflammation for months to years to support development of disease. The purpose of this research was to investigate the hypothesis that poorly soluble beryllium compounds release ions via dissolution in lung fluid. Dissolution kinetics of 17 poorly soluble particulate beryllium materials that span extraction through ceramics machining (ores, hydroxide, metal, copper-beryllium [CuBe] fume, oxides) and three CuBe alloy reference materials (chips, solid block) were measured over 31 d using artificial lung alveolar macrophage phagolysosomal fluid (pH 4.5). Differences in beryllium-containing particle physicochemical properties translated into differences in dissolution rates and lifetimes in artificial phagolysosomal fluid. Among all materials, dissolution rate constant values ranged from 10(-5) to 10(-10)gcm(-2)d(-1) and half-times ranged from tens to thousands of days. The presence of magnesium trisilicate in some beryllium oxide materials may have slowed dissolution rates. Materials associated with elevated prevalence of CBD had faster beryllium dissolution rates [10(-7)-10(-8)gcm(-2)d(-1)] than materials not associated with elevated prevalence (p<0.05).

  20. The dissolution behavior of scorodite in acidic environments

    NASA Astrophysics Data System (ADS)

    Pande, Preeti

    2001-11-01

    The safe disposal of arsenic-containing waste has been a difficult problem for the mining and metallurgical industry. One of the solutions to the arsenic problem is the precipitation of scorodite, an arsenic-containing mineral. Scorodite is reported to be relatively stable over a wide range of pH, and therefore may be a preferred disposal option. The effect of organic complexing agents on scorodite stability, however, is largely unknown. The present study is a phenomenological investigation into the dissolution kinetics of scorodite in the presence of oxalic acid under varying conditions of pH, oxalic acid concentration and temperature. The effect of scorodite particle size was also investigated. The morphological changes accompanying the dissolution process were examined by SEM and TEM analyses. Dissolution curves were divided into a linear induction period and a post-induction period. Activation energies were determined. Complete dissolution data were fit to the Prout-Tompkins/Austin-Rickett model. Dissolution data are indicative of auto-accelerated processes. The rapid increase in dissolution rate following the induction period is believed to be associated with an increase in the effective surface area. Pitting was observed on the surface of scorodite in the early stages of dissolution. In the later stages of dissolution, these pits were observed to grow and coalesce, in many cases resulting in the formation of dissolution holes.

  1. Dissolution rate measurements for resist processing in supercritical carbon dioxide

    NASA Astrophysics Data System (ADS)

    Pham, Victor Q.; Weibel, Gina L.; Rao, Nagesh G.; Ober, Christopher K.

    2002-07-01

    A dissolution rate monitor (DRM) was successfully constructed to study the behavior of thin photoresist films undergoing the dissolution process in supercritical carbon dioxide (SCCO2). The DRM is based on the principles of interferometry but requires special modifications to the processing vessel to allow for the passage of transmitted and reflected He-Ne laser light. Dissolution rates obtained agree well with independent profilometric measurements of film thickness loss. We found that for block and random copolymers of THPMA-F7MA, dissolution rates vary with film thickness, slowing down considerably towards the silicon surface. This behavior was also observed in TBMA-F7MA random copolymers.

  2. “Cleaning” the Surface of Hydroxyapatite Nanorods by a Reaction-Dissolution Approach

    PubMed Central

    Cao, Binrui; Wang, Lin; Xu, Hong; Zhu, Ye

    2015-01-01

    Synthetic nanoparticles are always terminated with coating molecules, which are often cytotoxic and not desired in biomedicine. Here we propose a novel reaction-dissolution approach to remove the cytotoxic coating molecules. A two-component solution is added to the nanoparticle solution; one component reacts with the coating molecules to form a salt whereas another is a solvent for dissolving and thus removing the salt. As a proof of concept, this work uses a NaOH-ethanol solution to remove the cytotoxic linoleic acid molecules coated on the hydroxyapatite nanorods (HAP-NRs). The removal of the coating molecules not only significantly improves the biocompatibility of HAP-NRs but also enables their oriented attachment into tightly-bound superstructures, which mimic the organized HAP crystals in bone and enamel and can promote the osteogenic differentiation of mesenchymal stem cells. Our reaction-dissolution approach can be extended to the surface “cleaning” of other nanomaterials. PMID:26693012

  3. Dissolution of different forms of partially porous silicon wafers under simulated physiological conditions

    NASA Astrophysics Data System (ADS)

    Anderson, S. H. C.; Elliott, H.; Wallis, D. J.; Canham, L. T.; Powell, J. J.

    2003-05-01

    Silicon (Si) in the form of orthosilicic acid (Si(OH)4) is vital for normal bone and connective tissue homeostasis. Porous Si films release Si(OH)4 in aqueous solutions in the physiological pH range. This study investigates the release of Si(OH)4 from porous Si films under physiological conditions with the aim of developing a bioavailable form of Si. Using a standardised technique, porous Si films released increasing Si with time. Dissolution was significant at pH 7 and above, and at a temperature of 37 °C. Higher porosity generally promoted dissolution, however multiple layer films did not show enhanced solubility over corresponding single layer controls. These properties will be used to optimise Si nanostructures that slowly deliver orthosilicic acid in the digestive tract.

  4. Dissolution of biogenic ooze over basement edifices in the equatorial Pacific with implications for hydrothermal ventilation of the oceanic crust

    USGS Publications Warehouse

    Bekins, B.A.; Spivack, A.J.; Davis, E.E.; Mayer, L.A.

    2007-01-01

    Recent observations indicate that curious closed depressions in carbonate sediments overlying basement edifices are widespread in the equatorial Pacific. A possible mechanism for their creation is dissolution by fluids exiting basement vents from off-axis hydrothermal flow. Quantitative analysis based on the retrograde solubility of calcium carbonate and cooling of basement fluids during ascent provides an estimate for the dissolution capacity of the venting fluids. Comparison of the dissolution capacity and fluid flux with typical equatorial Pacific carbonate mass accumulation rates shows that this mechanism is feasible. By maintaining sediment-free basement outcrops, the process may promote widespread circulation of relatively unaltered seawater in the basement in an area where average sediment thicknesses are 300-500 m. The enhanced ventilation can explain several previously puzzling observations in this region, including anomalously low heat flux, relatively unaltered seawater in the basement, and aerobic and nitrate-reducing microbial activity at the base of the sediments. ?? 2007 The Geological Society of America.

  5. VEGFR-2 conformational switch in response to ligand binding

    PubMed Central

    Sarabipour, Sarvenaz; Ballmer-Hofer, Kurt; Hristova, Kalina

    2016-01-01

    VEGFR-2 is the primary regulator of angiogenesis, the development of new blood vessels from pre-existing ones. VEGFR-2 has been hypothesized to be monomeric in the absence of bound ligand, and to undergo dimerization and activation only upon ligand binding. Using quantitative FRET and biochemical analysis, we show that VEGFR-2 forms dimers also in the absence of ligand when expressed at physiological levels, and that these dimers are phosphorylated. Ligand binding leads to a change in the TM domain conformation, resulting in increased kinase domain phosphorylation. Inter-receptor contacts within the extracellular and TM domains are critical for the establishment of the unliganded dimer structure, and for the transition to the ligand-bound active conformation. We further show that the pathogenic C482R VEGFR-2 mutant, linked to infantile hemangioma, promotes ligand-independent signaling by mimicking the structure of the ligand-bound wild-type VEGFR-2 dimer. DOI: http://dx.doi.org/10.7554/eLife.13876.001 PMID:27052508

  6. Influence of bulky yet flexible N-heterocyclic carbene ligands in gold catalysis

    PubMed Central

    Collado, Alba; Patrick, Scott R; Gasperini, Danila; Meiries, Sebastien

    2015-01-01

    Summary Three new Au(I) complexes of the formula [Au(NHC)(NTf2)] (NHC = N-heterocyclic carbene) bearing bulky and flexible ligands have been synthesised. The ligands studied are IPent, IHept and INon which belong to the ‘ITent’ (‘Tent’ for ‘tentacular’) family of NHC derivatives. The effect of these ligands in gold-promoted transformations has been investigated. PMID:26664600

  7. K Basin sludge dissolution engineering study

    SciTech Connect

    Westra, A.G.

    1998-08-28

    The purpose of this engineering study is to investigate the available technology related to dissolution of the K Basin sludge in nitric acid. The conclusion of this study along with laboratory and hot cell tests with actual sludge samples will provide the basis for beginning conceptual design of the sludge dissolver. The K Basin sludge contains uranium oxides, fragments of metallic U, and some U hydride as well as ferric oxyhydroxide, aluminum oxides and hydroxides, windblown sand that infiltrated the basin enclosure, ion exchange resin, and miscellaneous materials. The decision has been made to dispose of this sludge separate from the fuel elements stored in the basins. The sludge will be conditioned so that it meets Tank Waste Remediation System waste acceptance criteria and can be sent to one of the underground storage tanks. Sludge conditioning will be done by dissolving the fuel constituents in nitric acid, separating the insoluble material, adding neutron absorbers for criticality safety, and then reacting the solution with caustic to co-precipitate the uranium and plutonium. There will be five distinct feed streams to the sludge conditioning process two from the K East (KE) Basin and three from the K West (KW) Basin. The composition of the floor and pit sludges which contain more iron oxides and sand than uranium is much different than the canister sludges which are composed of mostly uranium oxides. The sludge conditioning equipment will be designed to process all of the sludge streams, but some of the operating parameters will be adjusted as necessary to handle the different sludge stream compositions. The volume of chemical additions and the amount of undissolved solids will be much different for floor and pit sludge than for canister sludge. Dissolution of uranium metal and uranium dioxide has been studied quite thoroughly and much information is available. Both uranium metal and uranium dioxide have been dissolved on a large scale in nuclear fuel

  8. Dissolution and compaction instabilities in geomaterials

    NASA Astrophysics Data System (ADS)

    Stefanou, I.; Sulem, J.; de Sauvage, J.

    2014-12-01

    Compaction bands play an important role in reservoir engineering and geological storage. Their presence in geological formations may also provide useful information on various geological processes. Several mechanisms can be involved at different scales and may be responsible for compaction band instabilities [1]. Compaction bands can be seen as a particular instability of the governing mathematical system leading to localization of deformation [2-4]. In a saturated porous rock, the progressive mechanical damage of the solid skeleton during compaction, results in the increase of the interface area of the reactants and consequently in the acceleration of the dissolution rate of the solid phase [2,5]. Thus, the solid skeleton is degraded more rapidly (mass removal because of dissolution), the overall mechanical properties of the system diminish (contraction of the elastic domain - chemical softening), deformations increase and the solid skeleton is further damaged (intergranular fractures, debonding, breakage of the porous network etc.). The stability of this positive feedback process is investigated analytically through linear stability analysis by considering the strong chemo-poro-mechanical coupling due to chemical dissolution. The post bifurcation behavior is then studied analytically and numerically revealing the compaction band thickness and periodicity. The effect of various parameters is studied as for instance the influence of the hydraulic diffusivity on the compaction band thickness. [1] P. Baud, S. Vinciguerra, C. David, A. Cavallo, E. Walker and T. Reuschlé (2009), Pure Appl. Geophys., 166(5-7), 869-898 [2] I. Stefanou and J. Sulem (2014), JGR: Solid Earth, 119(2), 880-899. doi:10.1002/2013JB010342I [3] J.W. Rudnicki and J.R. Rice (1975), Journal of the Mechanics and Physics of Solids 23(6),: 371-394 [4] K.A. Issen and J.W. Rudnicki (2000), JGR, 105(B9), 21529. doi:10.1029/2000JB900185 [5] R. Nova, R. Castellanza and C. Tamagnini (2003), International

  9. Dolomite Dissolution in Alkaline Cementious Media

    NASA Astrophysics Data System (ADS)

    Mittermayr, Florian; Klammer, Dietmar; Köhler, Stephan; Dietzel, Martin

    2010-05-01

    Chemical alteration of concrete has gained much attention over the past years as many cases of deterioration due to sulphate attack, thaumasite formation (TSA) or alkali silica reactions (ASR) have been reported in various constructions (Schmidt et al, 2009). Much less is known about the so called alkali carbonate reaction (ACR). It is believed that dolomite aggregates can react with the alkalis from the cement, dissolve and form calcite and brucite (Katayama, 2004). Due to very low solubility of dolomite in alkaline solutions this reaction seems doubtful. In this study we are trying to gain new insides about the conditions that can lead to the dissolution of dolomite in concrete. Therefore we investigated concrete samples from Austrian tunnels that show partially dissolved dolomite aggregates. Petrological analysis such as microprobe, SEM and Raman spectroscopy as well as a hydrochemical analysis of interstitial solutions and ground water and modelling with PhreeqC (Parkhurst and Appelo, 1999) are carried out. In addition a series of batch experiments is set up. Modelling approaches by PhreeqC show a thermodynamically possibility in the alkaline range when additional Ca2+ in solution causes dolomite to become more and more undersaturated as calcite gets supersaturated. Interacting ground water is enriched in Ca2+and saturated with respect to gypsum as marine evaporites are found in situ rocks. Furthermore it is more likely that Portlandite (Ca(OH)2) plays a more important role than Na and K in the cement. Portlandite acts as an additional Ca2+ source and is much more abundant than the alkalies. Some interstitial solutions are dominated mainly by Na+ and SO42- and reach concentrations up to 30 g/l TDS. It is believed that solutions can even reach thenardite saturation as efflorescences are found on the tunnel walls. In consequence dolomite solubility increases with increasing ionic strength. pH > 11 further accelerate the process of dedolomitization by the removal

  10. [Dissolution, absorption and bioaccumulation in gastrointestinal tract of mercury in HgS-containing traditional medicines Cinnabar and Zuotai].

    PubMed

    Zheng, Zhi-yuan; Li, Cen; Zhang, Ming; Yang, Hong-xia; Geng, Lu-jing; Li, Lin-shuai; Du, Yu-zhi; Wei, Li-xin

    2015-06-01

    α-HgS is the main component of traditional Chinese medicine cinnabar, while β-HgS is the main component of Tibetan medicine Zuotai. However, there was no comparative study on the dissolution and absorption in gastrointestinal tract and bioaccumulation in organs of mercury in Cinnabar, Zuotai, α-HgS and β-HgS. In this study, the dissolution process of the four compounds in the human gastrointestinal tract was simulated to determine the mercury dissolutions and compare the mercury dissolution of different medicines and the dissolution-promoting capacity of different solutions. To explore the absorption and bioaccumulation of cinnabar and Zuotai in organisms, mice were orally administered with clinical equivalent doses cinnabar and Zuotai. Meanwhile, a group of mice was given α-HgS and β-HgS with the equivalent mercury with cinnabar, while another group was given β-HgS and HgCl2 with the equivalent mercury with Zuotai. The mercury absorption and bioaccumulation capacities of different medicines in mice and their mercury bioaccumulation in different tissues and organs were compared. The experimental results showed a high mercury dissolutions of Zuotai in artificial gastrointestinal fluid, which was followed by β-HgS, cinnabar and α-HgS. As for the mercury absorption and bioaccumulation in mice, HgCl2 was the highest, β-HgS was the next, and a-HgS was slightly higher than cinnabar. The organs with the mercury bioaccumulation from high to low were kidney, liver and brain. This study is close to clinical practices and can provide reference for the clinical safe medication as well as a study model for the safety evaluation on heavy metal-containing medicines by observing the mercury dissolution, absorption, distribution and accumulation of mercury-containing medicines cinnabar and zuotai. PMID:26591542

  11. Bexarotene ligand pharmaceuticals.

    PubMed

    Hurst, R E

    2000-12-01

    Bexarotene (LGD-1069), from Ligand, was the first retinoid X receptor (RXR)-selective, antitumor retinoid to enter clinical trials. The company launched the drug for the treatment of cutaneous T-cell lymphoma (CTCL), as Targretin capsules, in the US in January 2000 [359023]. The company filed an NDA for Targretin capsules in June 1999, and for topical gel in December 1999 [329011], [349982] specifically for once-daily oral administration for the treatment of patients with early-stage CTCL who have not tolerated other therapies, patients with refractory or persistent early stage CTCL and patients with refractory advanced stage CTCL. The FDA approved Targretin capsules at the end of December 1999 for once-daily oral treatment of all stages of CTCL in patients refractory to at least one prior systemic therapy, at an initial dose of 300 mg/m2/day. After an NDA was submitted in December 1999 for Targretin gel, the drug received Priority Review status for use as a treatment of cutaneous lesions in patients with stage IA, IB or IIA CTCL [354836]. The FDA issued an approvable letter in June 2000, and granted marketing clearance for CTCL in the same month [370687], [372768], [372769], [373279]. Ligand had received Orphan Drug designation for this indication [329011]. At the request of the FDA, Ligand agreed to carry out certain post-approval phase IV and pharmacokinetic studies [351604]. The company filed an MAA with the EMEA for Targretin Capsules to treat lymphoma in November 1999 [348944]. The NDA for Targretin gel is based on a multicenter phase III trial that was conducted in the US, Canada, Europe and Australia involving 50 patients and a multicenter phase I/II clinical program involving 67 patients. Targretin gel was evaluated for the treatment of patients with early stage CTCL (IA-IIA) who were refractory to, intolerant to, or reached a response plateau for at least 6 months on at least two prior therapies. Efficacy results exceeded the protocol-defined response

  12. Dissolution test for silymarin tablets and capsules.

    PubMed

    Campodónico, A; Collado, E; Ricci, R; Pappa, H; Segall, A; Pizzorno, M T

    2001-01-01

    Silybine (SBN), isosilybine (ISBN), silycristine (SCN), silydianine (SDN), and taxifoline (TXF) are the main active flavonoids commonly found in the dried fruits of Silybum marianum, Gaertner (Compositae). Concentrations of these compounds, except TXF, are usually expressed together as silymarin content. This paper describes a simple dissolution test developed to estimate silymarin (Sl) in pharmaceutical formulations. Five commercial products were tested using this new method (including tablets, sugar tablets, and capsules): two from Argentina, one from Brazil, one from Spain, and one from Italy. Results demonstrated that, provided the dosage form disintegrates, amounts dissolved range from 50 to 90% of the labeled value. Products were analyzed by high performance liquid chromatography (HPLC) and UV spectrophotometry.

  13. Dissolution of bulk specimens of silicon nitride

    NASA Technical Reports Server (NTRS)

    Davis, W. F.; Merkle, E. J.

    1981-01-01

    An accurate chemical characterization of silicon nitride has become important in connection with current efforts to incorporate components of this material into advanced heat engines. However, there are problems concerning a chemical analysis of bulk silicon nitride. Current analytical methods require the pulverization of bulk specimens. A pulverization procedure making use of grinding media, on the other hand, will introduce contaminants. A description is given of a dissolution procedure which overcomes these difficulties. It has been found that up to at least 0.6 g solid pieces of various samples of hot pressed and reaction bonded silicon nitride can be decomposed in a mixture of 3 mL hydrofluoric acid and 1 mL nitric acid overnight at 150 C in a Parr bomb. High-purity silicon nitride is completely soluble in nitric acid after treatment in the bomb. Following decomposition, silicon and hydrofluoric acid are volatilized and insoluble fluorides are converted to a soluble form.

  14. Uranium Metal Analysis via Selective Dissolution

    SciTech Connect

    Delegard, Calvin H.; Sinkov, Sergey I.; Schmidt, Andrew J.; Chenault, Jeffrey W.

    2008-09-10

    Uranium metal, which is present in sludge held in the Hanford Site K West Basin, can create hazardous hydrogen atmospheres during sludge handling, immobilization, or subsequent transport and storage operations by its oxidation/corrosion in water. A thorough knowledge of the uranium metal concentration in sludge therefore is essential to successful sludge management and waste process design. The goal of this work was to establish a rapid routine analytical method to determine uranium metal concentrations as low as 0.03 wt% in sludge even in the presence of up to 1000-fold higher total uranium concentrations (i.e., up to 30 wt% and more uranium) for samples to be taken during the upcoming sludge characterization campaign and in future analyses for sludge handling and processing. This report describes the experiments and results obtained in developing the selective dissolution technique to determine uranium metal concentration in K Basin sludge.

  15. Helium enrichment during convective carbon dioxide dissolution

    NASA Astrophysics Data System (ADS)

    Larson, T.; Hesse, M. A.

    2013-12-01

    Motivated by observed variations of the CO2/He ratios in natural carbon dioxide (CO2) reservoirs, such as the Bravo Dome field in northeastern New Mexico, we have performed laboratory experiments equilibrating gas mixtures containing Helium (He) and CO2 with water, at close to ambient conditions in a closed system. The experimental design allows for continuous measurement of headspace pressure as well as timed interval measurements of the CO2/He ratios and the δ13C value of CO2 in the headspace. Results from three dissolution experiments are reported: 1) pure Helium system, 2) 98% CO2 + 2% Nitrogen system, and 3) 97% CO2 and 3% Helium. Final equilibrated experimental results are compared to theoretical results obtained using Henry's Law relationships. The evolution of the amount of dissolved CO2 computed from gas pressure and gas compositions are in good agreement with Henry's Law relationships. For example, the CO2 + N2 system was initially pressurized with pure CO2 to 1323 mbar and after six days it equilibrated to a measured headspace pressure of 596 mbar. This compares very well with a calculated equilibrium headspace pressure of 592 mbar for this system. The CO2 + He system was pressurized to 1398 mbar CO2 and after six days equilibrated to a measured headspace pressure of 397 mbar. This measured pressure is slightly higher than the predicted equilibrated headspace pressure of 341 mbar, indicating a possible leak in the system during this particular experiment. In both experiments the initial pH of the water was 9.3 and the final equilibrated pH was 5.4. The δ13C value of equilibrated headspace CO2 was within 0.25‰ of its starting δ13C value, demonstrating insignificant carbon isotope fractionation at low pH. Measured Helium/ CO2 ratios throughout the CO2+Helium experiment preserve a non-linear trend of increasing He/ CO2 ratios through time that correlate very well with the measured pressure drop from CO2 dissolution. This indicates that gas composition

  16. Noble gas and carbon isotopic evidence for CO2-driven silicate dissolution in a recent natural CO2 field

    NASA Astrophysics Data System (ADS)

    Dubacq, Benoît; Bickle, Mike J.; Wigley, Max; Kampman, Niko; Ballentine, Chris J.; Sherwood Lollar, Barbara

    2012-08-01

    Secure storage of anthropogenic carbon dioxide (CO2) in geological reservoirs requires predicting gas-water-rock interactions over millennial timescales. Noble gases and carbon isotope measurements can be used to shed light on the nature of competing dissolution-precipitation processes over different timescales, from the fast dissolution of gaseous CO2 in groundwater to more sluggish reactions involving dissolution and precipitation of newly formed minerals in the reservoir. Here we study a compilation of gas analyses including noble gases and δ13C of CO2 from nine different natural CO2 reservoirs. Amongst these reservoirs, the Bravo Dome CO2 field (New Mexico, USA) shows distinct geochemical trends which are explained by degassing of noble gases from groundwater altering the composition of the gas phase. This groundwater degassing is synchronous with the dissolution of CO2 in groundwater. Progressive creation of alkalinity via CO2-promoted mineral dissolution is required to explain the observed positive correlation between CO2/3He and δ13C of the gas phase, a unique feature of Bravo Dome. The differences between Bravo Dome and other natural CO2 reservoirs are likely explained by the more recent filling of Bravo Dome, reflecting CO2-water-rock interactions over thousands of years rather than over millions of years in older reservoirs.

  17. Effect of pulmonary surfactant on the dissolution, stability and uptake of zinc oxide nanowires by human respiratory epithelial cells.

    PubMed

    Theodorou, Ioannis G; Ruenraroengsak, Pakatip; Gow, Andrew; Schwander, Stephan; Zhang, Junfeng Jim; Chung, Kian Fan; Tetley, Teresa D; Ryan, Mary P; Porter, Alexandra E

    2016-11-01

    Inhaled nanoparticles (NPs) have high-deposition rates in the alveolar region of the lung but the effects of pulmonary surfactant (PS) on nanoparticle bioreactivity are unclear. Here, the impact of PS on the stability and dissolution of ZnO nanowires (ZnONWs) was investigated, and linked with their bioreactivity in vitro with human alveolar epithelial type 1-like cells (TT1). Pre-incubation of ZnONWs with Curosurf® (a natural porcine PS) decreased their dissolution at acidic pH, through the formation of a phospholipid corona. Confocal live cell microscopy confirmed that Curosurf® lowered intracellular dissolution, thus delaying the onset of cell death compared to bare ZnONWs. Despite reducing dissolution, Curosurf® significantly increased the uptake of ZnONWs within TT1 cells, ultimately increasing their toxicity after 24 h. Although serum improved ZnONW dispersion in suspension similar to Curosurf®, it had no effect on ZnONW internalization and toxicity, indicating a unique role of PS in promoting particle uptake. In the absence of PS, ZnONW length had no effect on dissolution kinetics or degree of cellular toxicity, indicating a less important role of length in determining ZnONW bioreactivity. This work provides unique findings on the effects of PS on the stability and toxicity of ZnONWs, which could be important in the study of pulmonary toxicity and epithelial-endothelial translocation of nanoparticles in general.

  18. Effect of pulmonary surfactant on the dissolution, stability and uptake of zinc oxide nanowires by human respiratory epithelial cells.

    PubMed

    Theodorou, Ioannis G; Ruenraroengsak, Pakatip; Gow, Andrew; Schwander, Stephan; Zhang, Junfeng Jim; Chung, Kian Fan; Tetley, Teresa D; Ryan, Mary P; Porter, Alexandra E

    2016-11-01

    Inhaled nanoparticles (NPs) have high-deposition rates in the alveolar region of the lung but the effects of pulmonary surfactant (PS) on nanoparticle bioreactivity are unclear. Here, the impact of PS on the stability and dissolution of ZnO nanowires (ZnONWs) was investigated, and linked with their bioreactivity in vitro with human alveolar epithelial type 1-like cells (TT1). Pre-incubation of ZnONWs with Curosurf® (a natural porcine PS) decreased their dissolution at acidic pH, through the formation of a phospholipid corona. Confocal live cell microscopy confirmed that Curosurf® lowered intracellular dissolution, thus delaying the onset of cell death compared to bare ZnONWs. Despite reducing dissolution, Curosurf® significantly increased the uptake of ZnONWs within TT1 cells, ultimately increasing their toxicity after 24 h. Although serum improved ZnONW dispersion in suspension similar to Curosurf®, it had no effect on ZnONW internalization and toxicity, indicating a unique role of PS in promoting particle uptake. In the absence of PS, ZnONW length had no effect on dissolution kinetics or degree of cellular toxicity, indicating a less important role of length in determining ZnONW bioreactivity. This work provides unique findings on the effects of PS on the stability and toxicity of ZnONWs, which could be important in the study of pulmonary toxicity and epithelial-endothelial translocation of nanoparticles in general. PMID:27441789

  19. Rapid Assessment of the Influence of Solution pH, Anion Concentration and Temperature on the Dissolution of Alloy 22

    SciTech Connect

    Gray, J J; Hayes, J R; Gdowski, G E; Viani, B E; Orme, C A

    2005-05-19

    We introduce an acid titration technique for the rapid characterization of the influence of solution pH, anion (such as chloride) concentration and temperature on the dissolution of metals. We demonstrate the technique with the characterization of the dissolution of alloy 22 (Ni-22Cr-13Mo-3W-3Fe) exposed to chloride-containing hydrochloric, sulfuric and nitric acid environments as a function of pH (from pH 5 to pH -1) and temperature (25-90 C). A combination of electrochemical techniques (electrochemical impedance spectroscopy and linear polarization resistance) and atomic force microscopy are used to characterize the influence of the various solutions on the dissolution of alloy 22. In solutions containing hydrochloric and sulfuric acids, a critical temperature exists for passive film breakdown on alloy 22 for all environments tested. Below the critical temperature, corrosion rates are less than 1 {micro}m/year. Above the critical temperature, the effect of temperature on dissolution rates is a function of both the pH and chloride content of the solution. In nitric acid containing solutions, the presence of nitrates promotes a stable passive oxide film that inhibits dissolution in all environments tested.

  20. Glass dissolution rate measurement and calculation revisited

    NASA Astrophysics Data System (ADS)

    Fournier, Maxime; Ull, Aurélien; Nicoleau, Elodie; Inagaki, Yaohiro; Odorico, Michaël; Frugier, Pierre; Gin, Stéphane

    2016-08-01

    Aqueous dissolution rate measurements of nuclear glasses are a key step in the long-term behavior study of such waste forms. These rates are routinely normalized to the glass surface area in contact with solution, and experiments are very often carried out using crushed materials. Various methods have been implemented to determine the surface area of such glass powders, leading to differing values, with the notion of the reactive surface area of crushed glass remaining vague. In this study, around forty initial dissolution rate measurements were conducted following static and flow rate (SPFT, MCFT) measurement protocols at 90 °C, pH 10. The international reference glass (ISG), in the forms of powders with different particle sizes and polished monoliths, and soda-lime glass beads were examined. Although crushed glass grains clearly cannot be assimilated with spheres, it is when using the samples geometric surface (Sgeo) that the rates measured on powders are closest to those found for monoliths. Overestimation of the reactive surface when using the BET model (SBET) may be due to small physical features at the atomic scale-contributing to BET surface area but not to AFM surface area. Such features are very small compared with the thickness of water ingress in glass (a few hundred nanometers) and should not be considered in rate calculations. With a SBET/Sgeo ratio of 2.5 ± 0.2 for ISG powders, it is shown here that rates measured on powders and normalized to Sgeo should be divided by 1.3 and rates normalized to SBET should be multiplied by 1.9 in order to be compared with rates measured on a monolith. The use of glass beads indicates that the geometric surface gives a good estimation of glass reactive surface if sample geometry can be precisely described. Although data clearly shows the repeatability of measurements, results must be given with a high uncertainty of approximately ±25%.

  1. Influence of rapeseed phospholipids on ibuprofen dissolution from solid dispersions.

    PubMed

    Sosada, M; Gorecki, M; Pasker, B

    2006-08-01

    The dissolution profiles of ibuprofen (IB) from solid dispersions prepared by the solvent evaporation method, containing the rapeseed lecithin ethanol soluble fraction (LESF) or rapeseed phosphatidylcholine (RPC) have been determined. The effect of incorporation of PEG 4,000 or PEG 8,000 in the solid dispersions on the controlled-release of IB was also investigated. Dissolution studies conducted in double-distilled water using the paddle dissolution apparatus showed that the initial dissolution rate (IDR) within the first 5 min and the maximum percent of dissolved IB of IB/LESF were double of those of IB/RPC (both in ratio 4:1 w/w). The low amounts of LESF markedly increased dissolution of IB. Increasing of LESF concentration from 0 to 10 and 20% in solid dispersions produced 60 and 100% improvement of IB maximum dissolution level respectively, to compare with that of IB alone. PEG 4,000 caused the slightly decreasing in IB dissolution rate, while PEG 8,000 markedly improved the dissolution of IB in examined conditions.

  2. Successful topical dissolution of cholesterol gallbladder stones using ethyl propionate.

    PubMed

    Hofmann, A F; Amelsberg, A; Esch, O; Schteingart, C D; Lyche, K; Jinich, H; Vansonnenberg, E; D'Agostino, H B

    1997-06-01

    Topical dissolution of cholesterol gallbladder stones using methyl tert-butyl ether (MTBE) is useful in symptomatic patients judged too ill for surgery. Previous studies showed that ethyl propionate (EP), a C5 ester, dissolves cholesterol gallstones rapidly in vitro, but differs from MTBE in being eliminated so rapidly by the liver that blood levels remain undetectable. Our aim was to test EP as a topical dissolution agent for cholesterol gallbladder stones. Five high-risk patients underwent topical dissolution of gallbladder stones by EP. In three patients, the solvent was instilled via a cholecystostomy tube placed previously to treat acute cholecystitis; in two patients, a percutaneous transhepatic catheter was placed in the gallbladder electively. Gallstone dissolution was assessed by chromatography, by gravimetry, and by catheter cholecystography. Total dissolution of gallstones was obtained in four patients after 6-10 hr of lavage; in the fifth patient, partial gallstone dissolution facilitated basketing of the stones. In two patients, cholesterol dissolution was measured and averaged 30 mg/min. Side effects were limited to one episode of transient hypotension and pain at the infusion site; no patient developed somnolence or nausea. Gallstone elimination was associated with relief of symptoms. EP is an acceptable alternative to MTBE for topical dissolution of cholesterol gallbladder stones in high-risk patients. The lower volatility and rapid hepatic extraction of EP suggest that it may be preferable to MTBE in this investigational procedure.

  3. 10 CFR 960.4-2-6 - Dissolution.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 4 2010-01-01 2010-01-01 false Dissolution. 960.4-2-6 Section 960.4-2-6 Energy DEPARTMENT OF ENERGY GENERAL GUIDELINES FOR THE PRELIMINARY SCREENING OF POTENTIAL SITES FOR A NUCLEAR WASTE REPOSITORY Postclosure Guidelines § 960.4-2-6 Dissolution. (a) Qualifying condition. The site shall...

  4. Dissolution Profile of Nimesulide from Pharmaceutical Preparations for Oral Use.

    PubMed

    Tubić, Biljana; Uzunović, Alija; Pilipović, Saša; Gagić, Žarko

    2016-01-01

    Nimesulide belongs to the group of semi-selective COX-2 inhibitors, widely used in solid oral formulations. In the present work the influence of surfactants among other drug excipients, as well as particle size of the active substance and the effects of medium pH on the dissolution rate of nimesulide from solid pharmaceutical forms. For that purpose, four different preparations containing 100 mg nimesulide per tablet and available in the market of Bosnia and Herzegovina (labeled here as A, B, C and D) were studied. The test for the assessment of dissolution profiles of the formulations was performed in surfactant-free dissolution medium pH 7.5. The dissolution profiles were compared by calculating difference (f1), and similarity (f2) factors. The increasing dissolution medium pH value from 7.5 to 7.75 resulted in a significant increase of nimesulide dissolution rate from the examined formulations. Also, the results showed that particle size affects to a great extent the dissolution rate and the best results were achieved with micronized nimesulide. The presence of the surfactants among the other excipients expressed a negligible effect on the dissolution profile.

  5. Setting dissolution specifications for modified-release dosage forms.

    PubMed

    Piscitelli, D A; Young, D

    1997-01-01

    Dissolution specifications are used for quality assurance and may also serve as a surrogate for in vivo bioavailability. These limits can guide formulation development and eliminate the need for bioavailability studies for scale up and post approval changes. Several methods for setting dissolution specifications have been reviewed in this chapter. A summary of the advantages and disadvantages for each method can be found in Table 1. When choosing a method for setting dissolution specifications, it is important to 1) have a discriminating dissolution system, 2) incorporate in vivo data, 3) include intersubject variability, and 4) predict plasma concentration-time profiles. Predicting plasma concentration curves allows one to see how the change in formulation or dissolution limits perform in vivo. Dissolution specifications should be set so that all formulations that have dissolution profiles within the limits of the specifications are bioequivalent. This can be assured if the boundaries are tested for bioequivalence. Minimally, the formulations that have dissolution profiles within the limits of the specifications should be bioequivalent to the pivotal batch. A population prediction of the plasma concentration-time profiles for the upper and lower limit would incorporate the true intersubject variability for the formulation. PMID:9269491

  6. 20 CFR 404.1219 - Dissolution of political subdivision.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 20 Employees' Benefits 2 2012-04-01 2012-04-01 false Dissolution of political subdivision. 404.1219 Section 404.1219 Employees' Benefits SOCIAL SECURITY ADMINISTRATION FEDERAL OLD-AGE, SURVIVORS AND... Agreements Is Obtained and Continues § 404.1219 Dissolution of political subdivision. If a...

  7. 20 CFR 404.1219 - Dissolution of political subdivision.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 20 Employees' Benefits 2 2014-04-01 2014-04-01 false Dissolution of political subdivision. 404.1219 Section 404.1219 Employees' Benefits SOCIAL SECURITY ADMINISTRATION FEDERAL OLD-AGE, SURVIVORS AND... Agreements Is Obtained and Continues § 404.1219 Dissolution of political subdivision. If a...

  8. 20 CFR 404.1219 - Dissolution of political subdivision.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 20 Employees' Benefits 2 2013-04-01 2013-04-01 false Dissolution of political subdivision. 404.1219 Section 404.1219 Employees' Benefits SOCIAL SECURITY ADMINISTRATION FEDERAL OLD-AGE, SURVIVORS AND... Agreements Is Obtained and Continues § 404.1219 Dissolution of political subdivision. If a...

  9. 20 CFR 404.1219 - Dissolution of political subdivision.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 20 Employees' Benefits 2 2011-04-01 2011-04-01 false Dissolution of political subdivision. 404.1219 Section 404.1219 Employees' Benefits SOCIAL SECURITY ADMINISTRATION FEDERAL OLD-AGE, SURVIVORS AND... Agreements Is Obtained and Continues § 404.1219 Dissolution of political subdivision. If a...

  10. 20 CFR 404.1219 - Dissolution of political subdivision.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 20 Employees' Benefits 2 2010-04-01 2010-04-01 false Dissolution of political subdivision. 404.1219 Section 404.1219 Employees' Benefits SOCIAL SECURITY ADMINISTRATION FEDERAL OLD-AGE, SURVIVORS AND... Agreements Is Obtained and Continues § 404.1219 Dissolution of political subdivision. If a...

  11. Thermal dissolution of maize starches in aqueous medium

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Starches are not soluble in neutral water at room temperature. However, if they are heated in a closed container beyond the boiling point of water, they eventually dissolve. The dissolution temperature depends on the type of starch. The dissolution process was monitored in real time by measuring ...

  12. 21 CFR 343.90 - Dissolution and drug release testing.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...-COUNTER HUMAN USE Testing Procedures § 343.90 Dissolution and drug release testing. (a) (b) Aspirin capsules. Aspirin capsules must meet the dissolution standard for aspirin capsules as contained in the United States Pharmacopeia (USP) 23 at page 132. (c) Aspirin delayed-release capsules and aspirin...

  13. 21 CFR 343.90 - Dissolution and drug release testing.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...-COUNTER HUMAN USE Testing Procedures § 343.90 Dissolution and drug release testing. (a) (b) Aspirin capsules. Aspirin capsules must meet the dissolution standard for aspirin capsules as contained in the United States Pharmacopeia (USP) 23 at page 132. (c) Aspirin delayed-release capsules and aspirin...

  14. 21 CFR 343.90 - Dissolution and drug release testing.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...-COUNTER HUMAN USE Testing Procedures § 343.90 Dissolution and drug release testing. (a) (b) Aspirin capsules. Aspirin capsules must meet the dissolution standard for aspirin capsules as contained in the United States Pharmacopeia (USP) 23 at page 132. (c) Aspirin delayed-release capsules and aspirin...

  15. 21 CFR 343.90 - Dissolution and drug release testing.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...-COUNTER HUMAN USE Testing Procedures § 343.90 Dissolution and drug release testing. (a) (b) Aspirin capsules. Aspirin capsules must meet the dissolution standard for aspirin capsules as contained in the United States Pharmacopeia (USP) 23 at page 132. (c) Aspirin delayed-release capsules and aspirin...

  16. 21 CFR 343.90 - Dissolution and drug release testing.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...-COUNTER HUMAN USE Testing Procedures § 343.90 Dissolution and drug release testing. (a) (b) Aspirin capsules. Aspirin capsules must meet the dissolution standard for aspirin capsules as contained in the United States Pharmacopeia (USP) 23 at page 132. (c) Aspirin delayed-release capsules and aspirin...

  17. Aluminum Target Dissolution in Support of the Pu-238 Program

    SciTech Connect

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W; Felker, Leslie Kevin; Mattus, Catherine H

    2014-09-01

    Selection of an aluminum alloy for target cladding affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the caustic dissolution step, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. We present a study to maximize dissolution of aluminum metal alloy, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. These data have been compared with published calculations of aluminum phase diagrams. Temperature logging during the transients has been investigated as a means to generate kinetic and mass transport data on the dissolution process. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.

  18. Convective dissolution of carbon dioxide in saline aquifers

    NASA Astrophysics Data System (ADS)

    Neufeld, Jerome A.; Hesse, Marc A.; Riaz, Amir; Hallworth, Mark A.; Tchelepi, Hamdi A.; Huppert, Herbert E.

    2010-11-01

    Geological carbon dioxide (CO2) storage is a means of reducing anthropogenic emissions. Dissolution of CO2 into the brine, resulting in stable stratification, increases storage security. The dissolution rate is determined by convection in the brine driven by the increase of brine density with CO2 saturation. We present a new analogue fluid system that reproduces the convective behaviour of CO2-enriched brine. Laboratory experiments and high-resolution numerical simulations show that the convective flux scales with the Rayleigh number to the 4/5 power, in contrast with a classical linear relationship. A scaling argument for the convective flux incorporating lateral diffusion from downwelling plumes explains this nonlinear relationship for the convective flux, provides a physical picture of high Rayleigh number convection in a porous medium, and predicts the CO2 dissolution rates in CO2 accumulations. These estimates of the dissolution rate show that convective dissolution can play an important role in enhancing storage security.

  19. Chlorite dissolution rates under CO2 saturated conditions from 50 to 120 °C and 120 to 200 bar CO2

    NASA Astrophysics Data System (ADS)

    Black, Jay R.; Haese, Ralf R.

    2014-01-01

    Chlorite dissolution rates were measured in a series of batch reactor experiments testing the effect of pCO2, pH, chloride and bicarbonate concentrations and temperature. Chlorite is an important diagenetic mineral in sedimentary basins, often found cementing mineral grains and filling pore space in formations that may serve as reservoirs for storing carbon dioxide. Conflicting reports of whether chlorite acts as a barrier to reservoir rock reactivity or leads to enhanced porosity due to dissolution, after the injection of supercritical CO2 into a reservoir, makes studying the reactivity of chlorite in contact with CO2 saturated waters pertinent. Measured dissolution rates were initially rapid and decreased over time as the saturation state of solution relative to chlorite increased. Temperature had the strongest effect on dissolution rate, with an apparent activation energy of 16 ± 0.5 kJ mol-1 and rate constant of log k0 = -9.56 ± 0.07 mol m-2 s-1 assuming a rate law of the form: rate = k0exp(-EA/RT). The apparent activation energy is lower than previously accepted values, but is consistent with a study of chlorite dissolution using flow through techniques (Smith et al., 2013). Mineral dissolution rates are typically proton enhanced, but the lack of a significant pH effect or pCO2 effect on chlorite dissolution rate in this study suggests that the use of NaHCO3 to buffer the pH of CO2 saturated solutions led to an inhibition of mineral dissolution in competition with the expected pH effect. This is supported by the observed dissolution rate increasing dramatically (half a log unit) with the use of an organic acid buffer (KHpthalate) under CO2 free conditions. The effect of chloride (NaCl ∼5 to 50 g/L) was found not to affect the dissolution rate of chlorite. Various empirical rate laws are proposed and fit to the data and lead to the development of a surface complex model describing proton promoted dissolution and bicarbonate inhibition of chlorite

  20. G4LDB: a database for discovering and studying G-quadruplex ligands

    PubMed Central

    Li, Qian; Xiang, Jun-Feng; Yang, Qian-Fan; Sun, Hong-Xia; Guan, Ai-Jiao; Tang, Ya-Lin

    2013-01-01

    The G-quadruplex ligands database (G4LDB, http://www.g4ldb.org) provides a unique collection of reported G-quadruplex ligands to streamline ligand/drug discovery targeting G-quadruplexes. G-quadruplexes are guanine-rich nucleic acid sequences in human telomeres and gene promoter regions. There is a growing recognition for their profound roles in a wide spectrum of diseases, such as cancer, diabetes and cardiovascular disease. Ligands that affect the structure and activity of G-quadruplexes can shed light on the search for G-quadruplex-targeting drugs. Therefore, we built the G4LDB to (i) compile a data set covering various physical properties and 3D structure of G-quadruplex ligands; (ii) provide Web-based tools for G-quadruplex ligand design; and (iii) to facilitate the discovery of novel therapeutic and diagnostic agents targeting G-quadruplexes. G4LDB currently contains >800 G-quadruplex ligands with ∼4000 activity records, which, to our knowledge, is the most extensive collection of its kind. It offers a user friendly interface that can meet a variety of data inquiries from researchers. For example, ligands can be searched for by name, molecular properties, structures, ligand activities and so on. Building on the reported data, the database also provides an online ligand design module that can predict ligand binding affinity in real time. PMID:23161677

  1. Carbonate ions and arsenic dissolution by groundwater

    USGS Publications Warehouse

    Kim, M.-J.; Nriagu, J.; Haack, S.

    2000-01-01

    solutions. The effects of pH and redox conditions on As dissolution were examined. Results showed that As was not leached significantly out of the Marshall Sandstone samples after 3 d using either deionized water or groundwater, but As was leached efficiently by sodium bicarbonate, potassium bicarbonate, and ferric chloride solutions. The leaching rate with sodium bicarbonate was about 25% higher than that with potassium bicarbonate. The data indicated that bicarbonate ion was involved primarily in As dissolution and that hydroxyl radical ion did not affect As dissolution to any significant degree. The amount of As leached was dependent upon the sodium bicarbonate concentration, increasing with reaction time for each concentration. Significant As leaching was found in the extreme pH ranges of <1.9 and 8.0-10.4. The resulting arseno-carbonate complexes formed were stable in groundwater.

  2. Instabilities in geomaterials induced by dissolution

    NASA Astrophysics Data System (ADS)

    Stefanou, I.; Sulem, J.

    2015-12-01

    Deformation bands play an important role in reservoir engineering, geological storage, underwater landslides and slow geological procedures. Various mechanisms can be involved at different scales and may be responsible for deformation bands. Mechanical and chemical degradation of the grain skeleton is a softening factor that can lead to compaction, shear or even dilation band formation [1]-[3]. The present study is twofold. On one hand it focuses on the mathematical modeling of chemically induced strain localization instabilities in porous rocks and on the other hand it explores the conditions for their creation [4], [5]. In a saturated porous rock, the progressive mechanical damage of the solid skeleton during deformation, results in the increase of the interface area of the reactants and consequently in the acceleration of the dissolution rate of the solid phase [6]. Under the presence of dissolving fluids the solid skeleton is degraded more rapidly (mass removal because of dissolution), the overall mechanical properties of the system diminish (contraction of the elastic domain - chemical softening), deformations increase and the solid skeleton is further damaged (intergranular fractures, debonding, breakage of the porous network etc.). Based on a micromechanical model, the conditions for deformation band triggering are investigated analytically. The heterogeneity of the microstructure in terms of chemical reactivity of the constituents of the REV is taken into account resulting in a characteristic internal length of the system. The post bifurcation behavior is finally studied both analytically and numerically revealing the thickness of the localized zone. References[1] I. Stefanou and J. Sulem, DOI: 10.1002/2013JB010342 [2] M. Cha and J. C. Santamarina, DOI: 10.1680/geot.14P.115 [3] M. D. Ingraham, K. A. Issen, and D. J. Holcomb, DOI: 10.1007/s11440-013-0275-y [4] K. A. Issen and J. W. Rudnicki, DOI: 10.1029/2000JB900185 [5] J. W. Rudnicki and J. R. Rice, DOI

  3. Tissue dissolution and modifications in dentin composition by different sodium hypochlorite concentrations

    PubMed Central

    TARTARI, Talita; BACHMANN, Luciano; MALIZA, Amanda Garcia Alves; ANDRADE, Flaviana Bombarda; DUARTE, Marco Antonio Hungaro; BRAMANTE, Clovis Monteiro

    2016-01-01

    ABSTRACT Sodium hypochlorite (NaOCl) remains the most used irrigation solution during root canal preparation because of characteristics such as wide-spectrum antimicrobial activity and organic tissue dissolution capacity. However, these solutions can alter dentin composition and there is no consensus on the optimal concentration of NaOCl to be used. Objectives To determine the organic matter dissolution and changes in dentin chemical composition promoted by different concentrations of NaOCl over time. Material and Methods: Fragments of bovine muscle tissue were weighed before and after 5, 10, and 15 min of immersion in the groups (n=10): G1- 0.9% saline solution; G2- 1% NaOCl; G3- 2.5% NaOCl; and G4- 5% NaOCl. Bovine dentin fragments were subjected to the same irrigants and absorption spectra were collected by Attenuated Total Reflectance of Fourier Transform Infrared Spectroscopy (ATR-FTIR) before and after 0,5, 1, 2, 3, 5, 8, and 10 min of immersion in the solutions. The ratios of the amide III/phosphate and carbonate/phosphate absorption bands were determined. The tissue dissolution and carbonate/phosphate ratios were submitted to the two-way analysis of variance (ANOVA) with Tukey’s multiple-comparison test (α<0.05) and to the one-way analysis of variance with Tukey’s (α<0.05). The amide III/phosphate ratio was analyzed by Friedman test (α<0.05) and the Kruskal-Wallis test with Dunn’s post-hoc (α<0.05). Results The increase in NaOCl concentration and contact time intensified the dissolution of organic matter and dentin collagen with reduction in the amide III/phosphate ratio. Significant differences between all groups (p<0.05) were observed in the dissolution of organic matter at 10 min and in the amide III/phosphate ratio between the saline solution and 5% NaOCl at 5 min. The carbonate/phosphate ratio decreased significantly in G2, G3, and G4 after 0,5 min of immersion (p<0.05), but more alterations did not occur in the subsequent periods (p>0

  4. Parameterization of phosphine ligands reveals mechanistic pathways and predicts reaction outcomes

    NASA Astrophysics Data System (ADS)

    Niemeyer, Zachary L.; Milo, Anat; Hickey, David P.; Sigman, Matthew S.

    2016-06-01

    The mechanistic foundation behind the identity of a phosphine ligand that best promotes a desired reaction outcome is often non-intuitive, and thus has been addressed in numerous experimental and theoretical studies. In this work, multivariate correlations of reaction outcomes using 38 different phosphine ligands were combined with classic potentiometric analyses to study a Suzuki reaction, for which the site selectivity of oxidative addition is highly dependent on the nature of the phosphine. These studies shed light on the generality of hypotheses regarding the structural influence of different classes of phosphine ligands on the reaction mechanism(s), and deliver a methodology that should prove useful in future studies of phosphine ligands.

  5. Bifunctional DTPA-type ligand

    SciTech Connect

    Gansow, O.A.; Brechbiel, M.W.

    1990-03-26

    The subject matter of the invention relates to bifunctional cyclohexyl DTPA ligands and methods of using these compounds. Specifically, such ligands are useful for radiolabeling proteins with radioactive metals, and can consequently be utilized with respect to radioimmunoimaging and/or radioimmunotherapy.

  6. The maximal affinity of ligands

    PubMed Central

    Kuntz, I. D.; Chen, K.; Sharp, K. A.; Kollman, P. A.

    1999-01-01

    We explore the question of what are the best ligands for macromolecular targets. A survey of experimental data on a large number of the strongest-binding ligands indicates that the free energy of binding increases with the number of nonhydrogen atoms with an initial slope of ≈−1.5 kcal/mol (1 cal = 4.18 J) per atom. For ligands that contain more than 15 nonhydrogen atoms, the free energy of binding increases very little with relative molecular mass. This nonlinearity is largely ascribed to nonthermodynamic factors. An analysis of the dominant interactions suggests that van der Waals interactions and hydrophobic effects provide a reasonable basis for understanding binding affinities across the entire set of ligands. Interesting outliers that bind unusually strongly on a per atom basis include metal ions, covalently attached ligands, and a few well known complexes such as biotin–avidin. PMID:10468550

  7. Dissolution rate measurements of TiN in Ti-6242

    SciTech Connect

    Bewlay, B.P.; Gigliotti, M.F.X.

    1997-01-01

    This paper describes measurements of the dissolution rate of nitrided Ti sponge and monolithic TiN rod in molten Ti-6242. The dissolution rate is described in terms of an interface recession rate that was 2.2 {micro}m/s for a Ti-6242 temperature of 1,725 C and dissolution times between 1 and 100 min. Similar dissolution rates were measured for nitrided sponge and monolithic rod. This report also descries the microstructural and chemical interdiffusion phenomena that occur during dissolution of solid {delta}TiN in molten Ti-6242. There is a N-containing solid {alpha}Ti layer and a N-solidified {beta}Ti layer between the solid {delta}TiN and liquid Ti-6242 during dissolution. Microprobe measurements indicate that diffusion of Al, Zr, Sn and Mo into {delta}TiN did not occur. Steep N concentration profiles were observed in the {alpha}Ti layer. Al, Zr, Sn and Mo were observed in the N-solidified {beta}Ti layer contained <1% N. Similar microstructural and interdiffusional behaviors were observed during dissolution of nitrided sponge and monolithic {delta}TiN rod in molten Ti-6242.

  8. Mechanism of dissolution inhibition in phenolic resins

    NASA Astrophysics Data System (ADS)

    Lin, Chen-Chy; Yeh, Tung-Feng; Reiser, Arnost; Honda, Kenji; Beauchemin, Bernard T., Jr.

    1993-09-01

    It was suggested in an earlier communication that dissolution inhibition in phenolic resins comes about through the blocking of some of the hydrophilic OH-groups by a hydrophobic effect of the inhibitors. Honda et al. have shown that the hydrophobicity of the additive is not a sufficient condition, and that the polar groups of the inhibitor, such as the diazoquinone function, play an important role in the inhibition effect. They found that additives with very similar skeletal structures, but differing in the polar anchor group, have very different inhibition efficiencies in a common novolac resin. In this study we investigate the interaction between phenols and the anchor groups of the inhibitors by determining the equilibrium constants of their association reaction. From this, the fraction of bound acceptor groups (inhibitors) can be estimated for the casting solution of the films at the point of solidification. It can be shown that this fraction correlates quite satisfactorily with the inhibition effect of the additives used in Honda's study.

  9. Dissolution of three insensitive munitions formulations.

    PubMed

    Taylor, Susan; Park, Eileen; Bullion, Katherine; Dontsova, Katerina

    2015-01-01

    The US military fires live munitions during training. To save soldiers lives both during training and war, the military is developing insensitive munitions (IM) that minimize unintentional detonations. Some of the compounds in the IM formulation are, however, very soluble in water, raising environmental concerns about their fate and transport. We measured the dissolution of three of these IM formulations, IMX101, IMX104 and PAX21 using laboratory drip tests and studied the accompanying changes in particle structure using micro computed tomography. Our laboratory drip tests mimic conditions on training ranges, where spatially isolated particles of explosives scattered by partial detonations are dissolved by rainfall. We found that the constituents of these IM formulations dissolve sequentially and in the order predicted by their aqueous solubility. The order of magnitude differences in solubility among their constituents produce water solutions whose compositions and concentrations vary with time. For IMX101 and IMX104, that contain 3-nitro-1,2,4-triazol-5-one (NTO), the solutions also vary in pH. The good mass balances measured for the drip tests indicate that the formulations are not being photo-or bio-transformed under laboratory conditions. PMID:25043961

  10. Dissolution and reduction of magnetite by bacteria

    NASA Technical Reports Server (NTRS)

    Kostka, J. E.; Nealson, K. H.

    1995-01-01

    Magnetite (Fe3O4) is an iron oxide of mixed oxidation state [Fe(II), Fe(III)] that contributes largely to geomagnetism and plays a significant role in diagenesis in marine and freshwater sediments. Magnetic data are the primary evidence for ocean floor spreading and accurate interpretation of the sedimentary magnetic record depends on an understanding of the conditions under which magnetite is stable. Though chemical reduction of magnetite by dissolved sulfide is well known, biological reduction has not been considered likely based upon thermodynamic considerations. This study shows that marine and freshwater strains of the bacterium Shewanella putrefaciens are capable of the rapid dissolution and reduction of magnetite, converting millimolar amounts to soluble Fe(II)in a few days at room temperature. Conditions under which magnetite reduction is optimal (pH 5-6, 22-37 degrees C) are consistent with an enzymatic process and not with simple chemical reduction. Magnetite reduction requires viable cells and cell contact, and it appears to be coupled to electron transport and growth. In a minimal medium with formate or lactate as the electron donor, more than 10 times the amount of magnetite was reduced over no carbon controls. These data suggest that magnetite reduction is coupled to carbon metabolism in S. putrefaciens. Bacterial reduction rates of magnetite are of the same order of magnitude as those estimated for reduction by sulfide. If such remobilization of magnetite occurs in nature, it could have a major impact on sediment magnetism and diagenesis.

  11. Cytotoxicity and intracellular dissolution of nickel nanowires.

    PubMed

    Perez, Jose E; Contreras, Maria F; Vilanova, Enrique; Felix, Laura P; Margineanu, Michael B; Luongo, Giovanni; Porter, Alexandra E; Dunlop, Iain E; Ravasi, Timothy; Kosel, Jürgen

    2016-09-01

    The assessment of cytotoxicity of nanostructures is a fundamental step for their development as biomedical tools. As widely used nanostructures, nickel nanowires (Ni NWs) seem promising candidates for such applications. In this work, Ni NWs were synthesized and then characterized using vibrating sample magnetometry, energy dispersive X-Ray analysis, and electron microscopy. After exposure to the NWs, cytotoxicity was evaluated in terms of cell viability, cell membrane damage, and induced apoptosis/necrosis on the model human cell line HCT 116. The influence of NW to cell ratio (10:1 to 1000:1) and exposure times up to 72 hours was analyzed for Ni NWs of 5.4 μm in length, as well as for Ni ions. The results show that cytotoxicity markedly increases past 24 hours of incubation. Cellular uptake of NWs takes place through the phagocytosis pathway, with a fraction of the dose of NWs dissolved inside the cells. Cell death results from a combination of apoptosis and necrosis, where the latter is the outcome of the secondary necrosis pathway. The cytotoxicity of Ni ions and Ni NWs dissolution studies suggest a synergistic toxicity between NW aspect ratio and dissolved Ni, with the cytotoxic effects markedly increasing after 24 hours of incubation. PMID:26692167

  12. Dissolution and reduction of magnetite by bacteria.

    PubMed

    Kostka, J E; Nealson, K H

    1995-10-01

    Magnetite (Fe3O4) is an iron oxide of mixed oxidation state [Fe(II), Fe(III)] that contributes largely to geomagnetism and plays a significant role in diagenesis in marine and freshwater sediments. Magnetic data are the primary evidence for ocean floor spreading and accurate interpretation of the sedimentary magnetic record depends on an understanding of the conditions under which magnetite is stable. Though chemical reduction of magnetite by dissolved sulfide is well known, biological reduction has not been considered likely based upon thermodynamic considerations. This study shows that marine and freshwater strains of the bacterium Shewanella putrefaciens are capable of the rapid dissolution and reduction of magnetite, converting millimolar amounts to soluble Fe(II)in a few days at room temperature. Conditions under which magnetite reduction is optimal (pH 5-6, 22-37 degrees C) are consistent with an enzymatic process and not with simple chemical reduction. Magnetite reduction requires viable cells and cell contact, and it appears to be coupled to electron transport and growth. In a minimal medium with formate or lactate as the electron donor, more than 10 times the amount of magnetite was reduced over no carbon controls. These data suggest that magnetite reduction is coupled to carbon metabolism in S. putrefaciens. Bacterial reduction rates of magnetite are of the same order of magnitude as those estimated for reduction by sulfide. If such remobilization of magnetite occurs in nature, it could have a major impact on sediment magnetism and diagenesis. PMID:11539843

  13. Dissolution of three insensitive munitions formulations.

    PubMed

    Taylor, Susan; Park, Eileen; Bullion, Katherine; Dontsova, Katerina

    2015-01-01

    The US military fires live munitions during training. To save soldiers lives both during training and war, the military is developing insensitive munitions (IM) that minimize unintentional detonations. Some of the compounds in the IM formulation are, however, very soluble in water, raising environmental concerns about their fate and transport. We measured the dissolution of three of these IM formulations, IMX101, IMX104 and PAX21 using laboratory drip tests and studied the accompanying changes in particle structure using micro computed tomography. Our laboratory drip tests mimic conditions on training ranges, where spatially isolated particles of explosives scattered by partial detonations are dissolved by rainfall. We found that the constituents of these IM formulations dissolve sequentially and in the order predicted by their aqueous solubility. The order of magnitude differences in solubility among their constituents produce water solutions whose compositions and concentrations vary with time. For IMX101 and IMX104, that contain 3-nitro-1,2,4-triazol-5-one (NTO), the solutions also vary in pH. The good mass balances measured for the drip tests indicate that the formulations are not being photo-or bio-transformed under laboratory conditions.

  14. Dissolution of oxygen-enriched Zircaloy-2

    NASA Astrophysics Data System (ADS)

    Oskarsson, M.; Ahlberg, E.; Pettersson, K.

    2001-10-01

    When metal is removed from oxidised Zircaloy specimens in order to study the morphology of the oxide at the metal-oxide interface needle-like features are frequently observed. Since similar features are not observed in cross-section TEM examinations it has been questioned whether or not the needles are a result of the dissolution process. In particular it has been proposed that reprecipitation of oxide may take place when the metal is enriched with oxygen. In the present work oxygen-enriched Zircaloy has been dissolved and the resulting structures examined. The results indicate that the needles are in fact artefacts of the specimen preparation procedure. However, there are no significant differences between oxygen-enriched and normal Zircaloy below an oxide layer grown in steam at about 400 °C. In view of the differences between the needle structure observed after metal removal with bromine or by electropolishing and removal by HF-HNO 3 pickling solution it is speculated that the needles consist of a hydrous zirconium oxide which is unstable in the pickling solution.

  15. Secondary calcification and dissolution respond differently to future ocean conditions

    NASA Astrophysics Data System (ADS)

    Silbiger, N. J.; Donahue, M. J.

    2014-09-01

    Climate change threatens both the accretion and erosion processes that sustain coral reefs. Secondary calcification, bioerosion, and reef dissolution are integral to the structural complexity and long-term persistence of coral reefs, yet these processes have received less research attention than reef accretion by corals. In this study, we use climate scenarios from RCP8.5 to examine the combined effects of rising ocean acidity and SST on both secondary calcification and dissolution rates of a natural coral rubble community using a flow-through aquarium system. We found that secondary reef calcification and dissolution responded differently to the combined effect of pCO2 and temperature. Calcification had a non-linear response to the combined effect of pCO2-temperature: the highest calcification rate occurred slightly above ambient conditions and the lowest calcification rate was in the highest pCO2-temperature condition. In contrast, dissolution increased linearly with pCO2-temperature. The rubble community switched from net calcification to net dissolution at +272 μatm pCO2 and 0.84 °C above ambient conditions, suggesting that rubble reefs may shift from net calcification to net dissolution before the end of the century. Our results indicate that dissolution may be more sensitive to climate change than calcification, and that calcification and dissolution have different functional responses to climate stressors, highlighting the need to study the effects of climate stressors on both calcification and dissolution to predict future changes in coral reefs.

  16. Secondary calcification and dissolution respond differently to future ocean conditions

    NASA Astrophysics Data System (ADS)

    Silbiger, N. J.; Donahue, M. J.

    2015-01-01

    Climate change threatens both the accretion and erosion processes that sustain coral reefs. Secondary calcification, bioerosion, and reef dissolution are integral to the structural complexity and long-term persistence of coral reefs, yet these processes have received less research attention than reef accretion by corals. In this study, we use climate scenarios from RCP 8.5 to examine the combined effects of rising ocean acidity and sea surface temperature (SST) on both secondary calcification and dissolution rates of a natural coral rubble community using a flow-through aquarium system. We found that secondary reef calcification and dissolution responded differently to the combined effect of pCO2 and temperature. Calcification had a non-linear response to the combined effect of pCO2 and temperature: the highest calcification rate occurred slightly above ambient conditions and the lowest calcification rate was in the highest temperature-pCO2 condition. In contrast, dissolution increased linearly with temperature-pCO2 . The rubble community switched from net calcification to net dissolution at +271 μatm pCO2 and 0.75 °C above ambient conditions, suggesting that rubble reefs may shift from net calcification to net dissolution before the end of the century. Our results indicate that (i) dissolution may be more sensitive to climate change than calcification and (ii) that calcification and dissolution have different functional responses to climate stressors; this highlights the need to study the effects of climate stressors on both calcification and dissolution to predict future changes in coral reefs.

  17. Dissolution retardation of solid silica during glass batch-melting

    SciTech Connect

    Hrma, Pavel R.; Marcial, Jose

    2011-07-15

    During glass-batch melting, solid silica (quartz) usually dissolves last. A retardation function was defined as a measure of the progressive inhibition of silica dissolution that occurs during batch melting. This function is based on the comparison of the measured rate of dissolution of silica particles with the hypothetical diffusion-controlled volume flux from regularly distributed particles with uniform concentration layers around them. The severe inhibition of silica dissolution has been attributed to the irregular spatial distribution of silica particles that is associated with the formation of nearly saturated melt at a portion of their surfaces. Irregular shapes and unequal sizes of particles also contribute to their extended lifetime.

  18. Calcite dissolution: an in situ study in the Panama Basin

    SciTech Connect

    Thunell, R.C.; Keir, R.S.; Honjo, S.

    1981-05-08

    The results of an in situ study of calcite dissolution in the Panama Basin indicate that the rate of dissolution in the water column increases suddenly below a water depth of about 2800 meters. This coincides with the depth at which the calcium carbonate content of surface sediments begins to decrease rapidly or the sedimentary lysocline. Since this level of increased dissolution both in the water column and on the sea floor does not appear to be related to the transition from supersaturation to undersaturation with respect to carbonate, there may be a kinetic origin for the lysocline in this region.

  19. A spatially resolved surface kinetic model for forsterite dissolution

    NASA Astrophysics Data System (ADS)

    Maher, Kate; Johnson, Natalie C.; Jackson, Ariel; Lammers, Laura N.; Torchinsky, Abe B.; Weaver, Karrie L.; Bird, Dennis K.; Brown, Gordon E.

    2016-02-01

    The development of complex alteration layers on silicate mineral surfaces undergoing dissolution is a widely observed phenomenon. Given the complexity of these layers, most kinetic models used to predict rates of mineral-fluid interactions do not explicitly consider their formation. As a result, the relationship between the development of the altered layers and the final dissolution rate is poorly understood. To improve our understanding of the relationship between the alteration layer and the dissolution rate, we developed a spatially resolved surface kinetic model for olivine dissolution and applied it to a series of closed-system experiments consisting of three-phases (water (±NaCl), olivine, and supercritical CO2) at conditions relevant to in situ mineral carbonation (i.e. 60 °C, 100 bar CO2). We also measured the corresponding δ26/24Mg of the dissolved Mg during early stages of dissolution. Analysis of the solid reaction products indicates the formation of Mg-depleted layers on the olivine surface as quickly as 2 days after the experiment was started and before the bulk solution reached saturation with respect to amorphous silica. The δ26/24Mg of the dissolved Mg decreased by approximately 0.4‰ in the first stages of the experiment and then approached the value of the initial olivine (-0.35‰) as the steady-state dissolution rate was approached. We attribute the preferential release of 24Mg to a kinetic effect associated with the formation of a Mg-depleted layer that develops as protons exchange for Mg2+. We used experimental data to calibrate a surface kinetic model for olivine dissolution that includes crystalline olivine, a distinct "active layer" from which Mg can be preferentially removed, and secondary amorphous silica precipitation. By coupling the spatial arrangement of ions with the kinetics, this model is able to reproduce both the early and steady-state long-term dissolution rates, and the kinetic isotope fractionation. In the early stages of

  20. Physiologically Based In vitro Models to Predict the Oral Dissolution and Absorption of a Solid Drug Delivery System.

    PubMed

    Li, Ziqiang; He, Xin

    2015-01-01

    To understand the sophisticated dynamic behaviors of drug elution and permeation in the gastrointestinal tract (GIT), researchers have tried to reemerge it by employing various in vitro experimental models. However, official in vitro apparatuses routinely used for quality control purposes, employ simple, non-physiologic buffers, and hydrodynamics conditions, and can not accurately perform continuous, dynamic in vivo pharmacokinetics (PK) behaviors. Therefore, different angles of GI physiology information are incorporate into novel models to forecast the dissolution and permeation of drug solid dosage forms. This review, in general, discusses some related studies of physiologically-based mechanical models to predict human absorption following oral administration in four sections. First the GIT, taken out of a complex physiological environment, where the drug is absorbed, distributed, metabolized and excreted (ADME) in the human body, is considered as the physiological basis for active pharmaceutics ingredients (API) dissolved and permeated through the epithelial cell. The second part embodies the theoretical foundation of in vitro models to predict human absorption and the corresponding in vitro.in vivo correlations (IVIVC). The third section summarizes physiologically based dissolution models developed recently, ranging from dynamic compartmental dissolution models, to biorelevant dissolution models based on certain physiological factors, to biphasic dissolution models. The last part is devoted to combined dissolution and absorption models that can be employed to simulate the continuous, dynamic behavior of oral drug delivery being dissolved and subsequently permeated across the GIT. Along with physiologically-based mechanically models spring up, pharmaceutical researchers will harvest better level A IVIVC for oral drug delivery systems, especially for sustained and controlled release preparations. On the other way hand, it will successively promote more effective

  1. DFT Study of Acceptorless Alcohol Dehydrogenation Mediated by Ruthenium Pincer Complexes: Ligand Tautomerization Governing Metal Ligand Cooperation.

    PubMed

    Hou, Cheng; Zhang, Zhihan; Zhao, Cunyuan; Ke, Zhuofeng

    2016-07-01

    Metal ligand cooperation (MLC) catalysis is a popular strategy to design highly efficient transition metal catalysts. In this presented theoretical study, we describe the key governing factor in the MLC mechanism, with the Szymczak's NNN-Ru and the Milstein's PNN-Ru complexes as two representative catalysts. Both the outer-sphere and inner-sphere mechanisms were investigated and compared. Our calculated result indicates that the PNN-Ru pincer catalyst will be restored to aromatic state during the catalytic cycle, which can be considered as the driving force to promote the MLC process. On the contrary, for the NNN-Ru catalyst, the MLC mechanism leads to an unfavored tautomerization in the pincer ligand, which explains the failure of the MLC mechanism in this system. Therefore, the strength of the driving force provided by the pincer ligand actually represents a prerequisite factor for MLC. Spectator ligands such as CO, PPh3, and hydride are important to ensure the catalyst follow a certain mechanism as well. We also evaluate the driving force of various bifunctional ligands by computational methods. Some proposed pincer ligands may have the potential to be the new pincer catalysts candidates. The presented study is expected to offer new insights for MLC catalysis and provide useful guideline for future catalyst design. PMID:27322755

  2. Mixed-ligand catalysts: a powerful tool in transition-metal- catalyzed cross-coupling reactions.

    PubMed

    Fan, Yuting; Cong, Mei; Peng, Ling

    2014-03-01

    Transition-metal-catalyzed cross-coupling reactions have fundamentally revolutionized organic synthesis, empowering the otherwise difficult to achieve products with rapid and convenient accesses alongside excellent yields. Within these reactions, ligands often play a critical role in specifically and effectively advocating the corresponding catalysis. Consequently, a myriad of ligands have been created and applied to make a fine tuning of electronic and steric effect of catalysts, remarkably promoting catalytic efficiency and applicability. The "mixed-ligand" concept has recently emerged; by combining and capitalizing on the superiority of each individual ligand already available, an expedient way can be achieved to reach a larger extent of catalytic diversity and efficacy. Given the availability of a wealth of ligands, it is reasonable to have great expectations for the original application of mixed-ligand catalytic systems and their important value in organic synthesis.

  3. Experimental dissolution vs. transformation of micas under acidic soil conditions: Clues from boron isotopes

    NASA Astrophysics Data System (ADS)

    Voinot, A.; Lemarchand, D.; Collignon, C.; Granet, M.; Chabaux, F.; Turpault, M.-P.

    2013-09-01

    Minerals in soils evolve through contact with water and other weathering agents (protons, organic acids and ligands) from the atmosphere or released by the surrounding vegetation and associated fauna. Determining the respective contribution of these agents to weathering budgets and the mechanisms by which they interact with soil minerals is a key step toward obtaining refined models of soil development, plant/mineral interactions and, ultimately, soil sustainability. To test the influence of different chemical agents on the processes of mica weathering (dissolution and transformation), we conducted a series of laboratory flow-through experiments on biotite using three chemical groups of reactants found in forest soils: protons (HCl), organic acids (citric acid) and ligands (siderophores). These experiments were performed at two different pH values (pH 3 and pH 4.5) for 37 days at 20 °C. Biotite was chosen as a test-mineral because it is reactive with acids and water and because it is commonly found in granite soils. To investigate the weathering reactions, the chemical and isotopic compositions of B (δ11B) and the concentrations of predominant cation (Si, Al, Mg, K and Fe) were monitored in the outflowing solutions. The choice of B as a proxy for weathering processes is based on the fact that B is located in different crystallographic sites in biotite (interlayers and structural sites, named I- and S-sites, respectively). We observed a large δ11B contrast between these sites (Δ11BS-I sites˜80‰), which allows for a precise quantification of the respective contribution of I- and S-sites to B released during biotite weathering. The individual reaction rates for these crystallographic sites were inferred from the B chemical and isotopic compositions of the outflowing solutions. A comparison with the major elements reveals that B is preferentially released to solution under all tested experimental conditions (up to 4 times more), particularly in the presence of

  4. Investigation on Microbial Dissolution of Uranium (VI) from Autunite Mineral - 13421

    SciTech Connect

    Sepulveda, Paola; Katsenovich, Yelena; Lagos, Leonel

    2013-07-01

    Precipitating autunite minerals by polyphosphate injection was identified as a feasible remediation strategy for sequestering uranium in contaminated groundwater and soil in situ at the Hanford Site. Autunite stability under vadose and saturated zone environmental conditions can help to determine the long-term effectiveness of this remediation strategy. The Arthrobacter bacteria are one of the most common groups in soils and are found in large numbers in Hanford soil as well as other subsurface environments contaminated with radionuclides. Ubiquitous in subsurface microbial communities, these bacteria can play a significant role in the dissolution of minerals and the formation of secondary minerals. The main objective of this investigation was to study the bacterial interactions under oxidizing conditions with uranium (VI); study the potential role of bicarbonate, which is an integral complexing ligand for U(VI) and a major ion in groundwater compositions; and present data from autunite dissolution experiments using Arthrobacter strain G968, a less U(VI)-tolerant strain. Sterile 100 mL glass mixed reactors served as the major bioreactor for initial experimentation. These autunite-containing bioreactors were injected with bacterial cells after the autunite equilibrated with the media solution amended with 0 mM, 3 mM 5 mM and 10 mM concentrations of bicarbonate. G968 Arthrobacter cells in the amount of 10{sup 6} cells/mL were injected into the reactors after 27 days, giving time for the autunite to reach steady state. Abiotic non-carbonate controls were kept without bacterial inoculation to provide a control for the biotic samples. Samples of the solution were analyzed for dissolved U(VI) by means of kinetic phosphorescence analyzer KPA-11 (Chemcheck Instruments, Richland, WA). Analysis showed that as [HCO{sub 3}{sup -}] increases, a diminishing trend on the effect of bacteria on autunite leaching is observed. Viability of cells was conducted after 24 hours of cell

  5. Dissolution kinetics and etch pit studies of potassium aluminium sulphate

    NASA Astrophysics Data System (ADS)

    van der Hoek, B.; Van Enckevort, W. J. P.; Van Der Linden, W. H.

    1983-03-01

    The dissolution process of the {111} faces of potash alum is studied, both by microtopographic examinations of the etch pit patterns and by measurement of the dissolution kinetics in a rotating disc crystallizer. Both methods showed that the Cabrera-Levine dissolution theory holds for the two most common dislocation types ending on the {111} faces of potash alum. On the basis of the rotating disc experiments, the interfacial supersaturation of the etch pit experiments was roughly estimated. Using this, it was found that at interfacial supersaturations below -0.6% (dislocations with <110> Burgers vector) or below -0.85% (dislocations with <100> Burgers vector) numerous etch pits related to those dislocation types appeared. Below those undersaturations the dissolution process is mainly determined by volume diffusion. From the critical undersaturation, determined in the rotating disc crystallizer, the value of the edge free energy of a step was found to be approximately 0.01 J/m 2.

  6. On the effects of subsurface parameters on evaporite dissolution (Switzerland)

    NASA Astrophysics Data System (ADS)

    Zidane, Ali; Zechner, Eric; Huggenberger, Peter; Younes, Anis

    2014-05-01

    Uncontrolled subsurface evaporite dissolution could lead to hazards such as land subsidence. Observed subsidences in a study area of Northwestern Switzerland were mainly due to subsurface dissolution (subrosion) of evaporites such as halite and gypsum. A set of 2D density driven flow simulations were evaluated along 1000 m long and 150 m deep 2D cross sections within the study area that is characterized by tectonic horst and graben structures. The simulations were conducted to study the effect of the different subsurface parameters that could affect the dissolution process. The heterogeneity of normal faults and its impact on the dissolution of evaporites is studied by considering several permeable faults that include non-permeable areas. The mixed finite element method (MFE) is used to solve the flow equation, coupled with the multipoint flux approximation (MPFA) and the discontinuous Galerkin method (DG) to solve the diffusion and the advection parts of the transport equation.

  7. Modeling solid-state transformations occurring in dissolution testing.

    PubMed

    Laaksonen, Timo; Aaltonen, Jaakko

    2013-04-15

    Changes in the solid-state form can occur during dissolution testing of drugs. This can often complicate interpretation of results. Additionally, there can be several mechanisms through which such a change proceeds, e.g. solvent-mediated transformation or crystal growth within the drug material itself. Here, a mathematical model was constructed to study the dissolution testing of a material, which undergoes such changes. The model consisted of two processes: the recrystallization of the drug from a supersaturated liquid state caused by the dissolution of the more soluble solid form and the crystal growth of the stable solid form at the surface of the drug formulation. Comparison to experimental data on theophylline dissolution showed that the results obtained with the model matched real solid-state changes and that it was able to distinguish between cases where the transformation was controlled either by solvent-mediated crystallization or solid-state crystal growth. PMID:23506958

  8. Solubility and dissolution profile assessment in drug discovery.

    PubMed

    Sugano, Kiyohiko; Okazaki, Arimichi; Sugimoto, Shohei; Tavornvipas, Sumitra; Omura, Atsushi; Mano, Takashi

    2007-08-01

    The purposes of the review are to: a) Provide a comprehensible introduction of the-state-of-the-art sciences of solubility and dissolution, b) introduce typical technologies to assess solubility and dissolution, and c) propose the best practice strategy. The theories of solubility and dissolution required in drug discovery were reviewed especially from the view point of oral absorption. The physiological conditions in the gastrointestinal fluid in humans and animals were then briefly summarized. Technologies to assess solubility and dissolution in drug discovery were then introduced. Recently, these technologies have been improved by the laboratory automation and computational technologies. Finally, the strategies to apply these technologies for a drug discovery project were discussed.

  9. In vivo dissolution measurement with indium-111 summation peak ratios

    SciTech Connect

    Jay, M.; Woodward, M.A.; Brouwer, K.R.

    1985-10-01

    Dissolution of (/sup 111/In)labeled tablets was measured in vivo in a totally noninvasive manner by using a modification of the perturbed angular correlation technique known as the summation peak ratio method. This method, which requires the incorporation of only 10-12 microCi into the dosage form, provided reliable dissolution data after oral administration of (/sup 111/In)lactose tablets. These results were supported by in vitro experiments which demonstrated that the dissolution rate as measured by the summation peak ratio method was in close agreement with the dissolution rate of salicylic acid in a (/sup 111/In)salicylic acid tablet. The method has the advantages of using only one detector, thereby avoiding the need for complex coincidence counting systems, requiring less radioactivity, and being potentially applicable to a gamma camera imaging system.

  10. Effect of alteration phase formation on the glass dissolution rate

    SciTech Connect

    Ebert, W.L.

    1997-10-01

    The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. It is important to understand the mechanism by which alteration phases affect glass corrosion behavior and the glass dissolution rate to reliably predict whether or not similar effects will occur in a disposal environment and the impact of phase formation on the long-term performance of waste glass. While solid state transformation of a glass to thermodynamically more stable phases in kinetically prohibitive, contact by water provides an energetically favorable pathway for this transformation to occur by a dissolution-reprecipitation mechanism. The kinetics of the transformation depends on the dissolution kinetics of the glass and the precipitation kinetics of the alteration phases. The rates of these two processes are linked primarily through the solution activity of orthosilicic acid (and perhaps also that of an aluminum-bearing species).

  11. Sticky physics of joy: on the dissolution of spherical candies

    NASA Astrophysics Data System (ADS)

    Windisch, Andreas; Windisch, Herbert; Windisch, Anita

    2013-03-01

    Assuming a constant mass decrease per unit surface and unit time we provide a very simplistic model for the dissolution process of spherical candies. The aim is to investigate the quantitative behaviour of the dissolution process throughout the act of eating the candy. In our model we do not take any microscopic mechanism of the dissolution process into account, but rather provide an estimate which is based on easy-to-follow calculations. Having obtained a description based on this calculation, we confirm the assumed behaviour by providing experimental data for the dissolution process. Besides a deviation from our prediction caused by the production process of the candies below a diameter of 2 mm, we find good agreement with our model-based expectations. Delicate questions on the optimal strategy for enjoying a candy will be addressed, such as whether it is wise to split the candy by breaking it with the teeth or not.

  12. TANK 12 SLUDGE CHARACTERIZATION AND ALUMINUM DISSOLUTION DEMONSTRATION

    SciTech Connect

    Reboul, S; Michael Hay, M; Kristine Zeigler, K; Michael Stone, M

    2009-03-25

    A 3-L sludge slurry sample from Tank 12 was characterized and then processed through an aluminum dissolution demonstration. The dominant constituent of the sludge was found to be aluminum in the form of boehmite. The iron content was minor, about one-tenth that of the aluminum. The salt content of the supernatant was relatively high, with a sodium concentration of {approx}7 M. Due to these characteristics, the yield stress and plastic viscosity of the unprocessed slurry were relatively high (19 Pa and 27 cP), and the settling rate of the sludge was relatively low ({approx}20% settling over a two and a half week period). Prior to performing aluminum dissolution, plutonium and gadolinium were added to the slurry to simulate receipt of plutonium waste from H-Canyon. Aluminum dissolution was performed over a 26 day period at a temperature of 65 C. Approximately 60% of the insoluble aluminum dissolved during the demonstration, with the rate of dissolution slowing significantly by the end of the demonstration period. In contrast, approximately 20% of the plutonium and less than 1% of the gadolinium partitioned to the liquid phase. However, about a third of the liquid phase plutonium became solubilized prior to the dissolution period, when the H-Canyon plutonium/gadolinium simulant was added to the Tank 12 slurry. Quantification of iron dissolution was less clear, but appeared to be on the order of 1% based on the majority of data (a minor portion of the data suggested iron dissolution could be as high as 10%). The yield stress of the post-dissolution slurry (2.5 Pa) was an order of magnitude lower than the initial slurry, due most likely to the reduced insoluble solids content caused by aluminum dissolution. In contrast, the plastic viscosity remained unchanged (27 cP). The settling rate of the post-dissolution slurry was higher than the initial slurry, but still relatively low compared to settling of typical high iron content/low salt content sludges. Approximately 40

  13. Tank 12 Sludge Characterization and Aluminum Dissolution Demonstration

    SciTech Connect

    Reboul, S.; Hay, M.; Zeigler, K; Stone, M.

    2010-05-05

    A 3-L sludge slurry sample from Tank 12 was characterized and then processed through an aluminum dissolution demonstration. The dominant constituent of the sludge was found to be aluminum in the form of boehmite. The iron content was minor, about one-tenth that of the aluminum. The salt content of the supernatant was relatively high, with a sodium concentration of {approx}7 M. Due to these characteristics, the yield stress and plastic viscosity of the unprocessed slurry were relatively high (19 Pa and 27 cP), and the settling rate of the sludge was relatively low ({approx}20% settling over a two and a half week period). Prior to performing aluminum dissolution, plutonium and gadolinium were added to the slurry to simulate receipt of plutonium waste from H-Canyon. Aluminum dissolution was performed over a 26 day period at a temperature of 65 C. Approximately 60% of the insoluble aluminum dissolved during the demonstration, with the rate of dissolution slowing significantly by the end of the demonstration period. In contrast, approximately 20% of the plutonium and less than 1% of the gadolinium partitioned to the liquid phase. However, about a third of the liquid phase plutonium became solubilized prior to the dissolution period, when the H-Canyon plutonium/gadolinium simulant was added to the Tank 12 slurry. Quantification of iron dissolution was less clear, but appeared to be on the order of 1% based on the majority of data (a minor portion of the data suggested iron dissolution could be as high as 10%). The yield stress of the post-dissolution slurry (2.5 Pa) was an order of magnitude lower than the initial slurry, due most likely to the reduced insoluble solids content caused by aluminum dissolution. In contrast, the plastic viscosity remained unchanged (27 cP). The settling rate of the post-dissolution slurry was higher than the initial slurry, but still relatively low compared to settling of typical high iron content/low salt content sludges. Approximately 40

  14. Dissolution of olivine in basaltic liquids: experimental observations and applications.

    USGS Publications Warehouse

    Thornber, C.R.; Huebner, J.S.

    1985-01-01

    Rates of olivine dissolution in synthetic lunar basalt 77115 and a silica-enriched 77115 composition (Sil-77115) at superliquidus temperatures have been determined. Dissolution-rate data have been applied to the problem of the thermal history of fragment-laden impact-melt rocks of the lunar highlands. Textural and chemical criteria are discussed for the recognition of olivine resorption (and growth) phenomena in igneous rocks. -J.A.Z.

  15. The effect of fuel chemistry on UO2 dissolution

    NASA Astrophysics Data System (ADS)

    Casella, Amanda; Hanson, Brady; Miller, William

    2016-08-01

    The dissolution rate of both unirradiated UO2 and used nuclear fuel has been studied by numerous countries as part of the performance assessment of proposed geologic repositories. In the scenario of waste package failure and groundwater contact with the fuel, the effects of variables such as temperature, dissolved oxygen, and water and fuel chemistry on the dissolution rates of the fuel are necessary to provide a quantitative estimate of the potential release over geologic time frames. The primary objective of this research was to determine the influence these parameters, with primary focus on the fuel chemistry, have on the dissolution rate of unirradiated UO2 under oxidizing repository conditions and compare them to the rates predicted by current dissolution models. Both unirradiated UO2 and UO2 doped with varying concentrations of Gd2O3, to simulate used fuel composition after long time periods when radiolysis has minor contributions to dissolution, were examined. In general, a rise in temperature increased the dissolution rate of UO2 and had a larger effect on pure UO2 than on those doped with Gd2O3. Oxygen dependence was observed in the UO2 samples with no dopant and increased as the temperature rose; in the doped fuels less dependence was observed. The addition of gadolinia into the UO2 matrix resulted in a significant decrease in the dissolution rate. The matrix stabilization effect resulting from the dopant proved even more beneficial in lowering the dissolution rate at higher temperatures and dissolved O2 concentrations in the leachate where the rates would typically be elevated.

  16. Two-phase convective CO2 dissolution in saline aquifers

    DOE PAGESBeta

    Martinez, Mario J.; Hesse, Marc A.

    2016-01-01

    Geologic carbon storage in deep saline aquifers is a promising technology for reducing anthropogenic emissions into the atmosphere. Dissolution of injected CO2 into resident brines is one of the primary trapping mechanisms generally considered necessary to provide long-term storage security. Given that diffusion of CO2 in brine is woefully slow, convective dissolution, driven by a small increase in brine density with CO2 saturation, is considered to be the primary mechanism of dissolution trapping. Previous studies of convective dissolution have typically only considered the convective process in the single-phase region below the capillary transition zone and have either ignored the overlyingmore » two-phase region where dissolution actually takes place or replaced it with a virtual region with reduced or enhanced constant permeability. Our objective is to improve estimates of the long-term dissolution flux of CO2 into brine by including the capillary transition zone in two-phase model simulations. In the fully two-phase model, there is a capillary transition zone above the brine-saturated region over which the brine saturation decreases with increasing elevation. Our two-phase simulations show that the dissolution flux obtained by assuming a brine-saturated, single-phase porous region with a closed upper boundary is recovered in the limit of vanishing entry pressure and capillary transition zone. For typical finite entry pressures and capillary transition zone, however, convection currents penetrate into the two-phase region. As a result, this removes the mass transfer limitation of the diffusive boundary layer and enhances the convective dissolution flux of CO2 more than 3 times above the rate assuming single-phase conditions.« less

  17. Two-phase convective CO2 dissolution in saline aquifers

    DOE PAGESBeta

    Martinez, Mario J.; Hesse, Marc A.

    2016-01-30

    Geologic carbon storage in deep saline aquifers is a promising technology for reducing anthropogenic emissions into the atmosphere. Dissolution of injected CO2 into resident brines is one of the primary trapping mechanisms generally considered necessary to provide long-term storage security. Given that diffusion of CO2 in brine is woefully slow, convective dissolution, driven by a small increase in brine density with CO2 saturation, is considered to be the primary mechanism of dissolution trapping. Previous studies of convective dissolution have typically only considered the convective process in the single-phase region below the capillary transition zone and have either ignored the overlyingmore » two-phase region where dissolution actually takes place or replaced it with a virtual region with reduced or enhanced constant permeability. Our objective is to improve estimates of the long-term dissolution flux of CO2 into brine by including the capillary transition zone in two-phase model simulations. In the fully two-phase model, there is a capillary transition zone above the brine-saturated region over which the brine saturation decreases with increasing elevation. Our two-phase simulations show that the dissolution flux obtained by assuming a brine-saturated, single-phase porous region with a closed upper boundary is recovered in the limit of vanishing entry pressure and capillary transition zone. For typical finite entry pressures and capillary transition zone, however, convection currents penetrate into the two-phase region. As a result, this removes the mass transfer limitation of the diffusive boundary layer and enhances the convective dissolution flux of CO2 more than 3 times above the rate assuming single-phase conditions.« less

  18. Experimental results: Pilot plant calcine dissolution and liquid feed stability

    SciTech Connect

    Herbst, R.S.; Fryer, D.S.; Brewer, K.N.; Johnson, C.K.; Todd, T.A.

    1995-02-01

    The dissolution of simulated Idaho Chemical Processing Plant pilot plant calcines, containing none of the radioactive actinides, lanthanides or fission products, was examined to evaluate the solubility of calcine matrix materials in acidic media. This study was a necessary precursor to dissolution and optimization experiments with actual radionuclide-containing calcines. The importance of temperature, nitric acid concentration, ratio of acid volume to calcine mass, and time on the amount, as a weight percentage of calcine dissolved, was evaluated. These parameters were studied for several representative pilot plant calcine types: (1) Run No. 74 Zirconia calcine; (2) Run No. 17 Zirconia/Sodium calcine; (3) Run No. 64 Zirconia/Sodium calcine; (3) Run No. 1027 Alumina calcine; and (4) Run No. 20 Alumina/Zirconia/Sodium calcine. Statistically designed experiments with the different pilot plant calcines indicated the effect of the studied process variables on the amount of calcine dissolved decreases in the order: Acid/Calcine Ratio > Temperature > HNO{sub 3} Concentration > Dissolution Time. The following conditions are suitable to achieve greater than 90 wt. % dissolution of most Zr, Al, or Na blend calcines: (1) Maximum nitric acid concentration of 5M; (2) Minimum acid/calcine ratio of 10 mL acid/1 gram calcine; (3) Minimum dissolution temperature of 90{degrees}C; and (4) Minimum dissolution time of 30 minutes. The formation of calcium sulphate (CaSO{sub 4}) precipitates was observed in certain dissolved calcine solutions during the dissolution experiments. Consequently, a study was initiated to evaluate if and under what conditions the resulting dissolved calcine solutions would be unstable with regards to precipitate formation. The results indicate that precipitate formation in the calcine solutions prepared under the above proposed dissolution conditions are not anticipated.

  19. Dissolution test for ivermectin in oral veterinary paste.

    PubMed

    Sznitowska, M; Pietkiewicz, J; Stokrocka, M; Janicki, S

    2004-10-01

    A dissolution test for oral veterinary pastes with ivermectin using the Ph. Eur. paddle apparatus was developed. Sink conditions were achieved with sodium lauryl sulphate in a concentration of 0.5% as dissolution medium. By means of HPLC fast degradation of ivermectin was observed in HCl 0.1 M solution. Rotation speed of the paddle at 75 rpm was appropriate as demonstrated in a study comparing two different products. PMID:15544065

  20. Boehmite Dissolution Studies Supporting High Level Waste Pretreatment - 9383

    SciTech Connect

    Peterson, Reid A.; Russell, Renee L.; Snow, Lanee A.

    2009-03-01

    Boehmite is present in significant quantities in several of the Hanford waste tanks. It has been proposed that the boehmite will be dissolved through caustic leaching in the Hanford Waste Treatment Plant currently under construction. Therefore, it is important to fully understand the nature of this dissolution so that the process can be deployed. This research determined the impact of primary control parameters on the boehmite dissolution rate. The impact of aluminate ion on the dissolution kinetics was determined. In addition, other parameters that impact boehmite dissolution, such as free hydroxide concentration and reaction temperature, were also assessed and used to develop a semi-empirical model of the boehmite dissolution process. The understanding derived from this work will be used as the basis to evaluate and improve the planned performance of the Hanford Waste Treatment plant. This work is the first in a series of programs aimed at demonstrating the Waste Treatment Plant dissolution process. This work will be used to develop a simulant of the boehmite-containing Hanford waste. That simulant will then be used in laboratory- and pilot-scale testing to demonstrate the Waste Treatment Plant pretreatment process in an integrated fashion.

  1. Kinetics and mechanism of photopromoted oxidative dissolution of antimony trioxide.

    PubMed

    Hu, Xingyun; Kong, Linghao; He, Mengchang

    2014-12-16

    Light (sunlight, ultraviolet, simulated sunlight) irradiation was used to initiate the dissolution of antimony trioxide (Sb2O3). Dissolution rate of Sb2O3 was accelerated and dissolved trivalent antimony (Sb(III)) was oxidized in the irradiation of light. The photopromoted oxidative dissolution mechanism of Sb2O3 was studied through experiments investigating the effects of pH, free radicals scavengers, dissolved oxygen removal and Sb2O3 dosage on the release rate of antimony from Sb2O3 under simulated sunlight irradiation. The key oxidative components were hydroxyl free radicals, photogenerated holes and superoxide free radicals; their contribution ratios were roughly estimated. In addition, a conceptual model of the photocatalytic oxidation dissolution of Sb2O3 was proposed. The overall pH-dependent dissolution rate of Sb2O3 and the oxidation of Sb(III) under light irradiation were expressed by r = 0.08 ·[OH(-)](0.63) and rox = 0.10 ·[OH(-)](0.79). The present study on the mechanism of the photo-oxidation dissolution of Sb2O3 could help clarify the geochemical cycle and fate of Sb in the environment.

  2. Organic phase resistance to dissolution of polycyclic aromatic hydrocarbon compounds

    SciTech Connect

    Ortiz, E.; Kraatz, M.; Luthy, R.G.

    1999-01-15

    The dissolution of naphthalene, phenanthrene, and pyrene from viscous organic phases into water was studied in continuous-flow systems for time periods ranging from several months to more than 1 year. By selecting nonaqueous phases ranging from low viscosity to semisolid, i.e., from a light lubricating oil to paraffin, the governance of mass transfer was shown to vary from water phase control to nonaqueous phase control. An advancing depleted-zone model is proposed to explain the dissolution of PAHs from a viscous organic phase wherein the formation of a depleted zone within the organic phase increases the organic phase resistance to the dissolution of PAHs. The experimental data suggest the formation of a depleted zone within the organic phase for systems comprising a high-viscosity oil, petrolatum (petroleum jelly), and paraffin. Organic phase resistance to naphthalene dissolution became dominant over aqueous phase resistance after flushing for several days. Such effects were not evident for low viscosity lubricating oil. The transition from aqueous-phase dissolution control to nonaqueous-phase dissolution control appears predictable, and this provides a more rational framework to assess long-term release of HOCs from viscous nonaqueous phase liquids and semisolids.

  3. Enhanced CO2 Dissolution in Heterogeneous Porous Media

    NASA Astrophysics Data System (ADS)

    Daniels, K.; Neufeld, J. A.; Bickle, M. J.; Hallworth, M. A.

    2014-12-01

    Long-term and secure geological storage of CO2 through technologies such as Carbon Capture and Storage (CCS) within reservoirs is seen as a technological means to reduce anthropogenic CO2 emissions. The long-term viability of this technology is reliant on the structural and secondary trapping of supercritical CO2 within heterogeneous reservoirs. Secondary trapping, primarily through the dissolution of CO2 into ambient reservoir brine to produce a denser fluid, is capable of retaining CO2 in the subsurface and thus reducing the risks of storage. To model secondary trapping we need to understand how the flow of CO2 through heterogeneous reservoir rocks enhances dissolution of supercritical CO2 in reservoir brines. Here we experimentally investigate the dissolution of CO2 in reservoir brines in layered, heterogeneous geological formations. Using analogue experiments, designed to approximate an enhanced oil recovery (EOR) setting, the processes of mixing, dispersion and dissolution are examined. These are compared against test results from non-layered, homogeneous porous media experiments. We find that heterogeneities significantly enhance mixing, particularly between adjacent porous layers. During fluid propagation, pore-scale viscous fingers grow and retreat, thereby providing an increased surface area between the flow and the ambient reservoir fluid. This enhanced mixing is predicted to substantially increase the dissolution of CO2 in reservoir brines. Both permeability and viscosity differences are found to have a significant effect on the interface between the two fluids, and therefore the likely amount of dissolution of CO2.

  4. Oral dosage form performance tests: new dissolution approaches.

    PubMed

    Hauck, Walter W; Foster, Thomas; Sheinin, Eric; Cecil, Todd; Brown, William; Marques, Margareth; Williams, Roger L

    2005-02-01

    The performance test is one of a series of tests that compose the specification in a United States Pharmacopeia (USP) dosage form monograph. For an orally administered, nonsolution dosage form, it is usually satisfied by either a dissolution or disintegration procedure. Dissolution acceptance criteria are usually set in private negotiations between an applicant and a regulatory agency. With information about this private agreement and other information provided in a sponsor's Request for Revision to USP, the USP's Council of Experts elaborates a public dosage form monograph. Based on the relationship between the regulatory decisions and the Request for Revision, the USP dissolution procedure links to a regulatory judgment about bioavailability and bioequivalence and, ultimately, to a judgment about safety and efficacy. The current dissolution procedure and acceptance criteria are perceived as having worked well over the years and are generally accepted. This article discusses new approaches that merit consideration. These approaches focus on a) explicit use of hypothesis testing, b) use of parametric tolerance intervals, c) improved ways to set dissolution acceptance criteria, and d) a more flexible protocol to assess conformity. Application of the proposed approaches may better assess, manage, and communicate both manufacturer and consumer risk for dissolution testing.

  5. Oxidative dissolution of silver nanoparticles: A new theoretical approach.

    PubMed

    Adamczyk, Zbigniew; Oćwieja, Magdalena; Mrowiec, Halina; Walas, Stanisław; Lupa, Dawid

    2016-05-01

    A general model of an oxidative dissolution of silver particle suspensions was developed that rigorously considers the bulk and surface solute transport. A two-step surface reaction scheme was proposed that comprises the formation of the silver oxide phase by direct oxidation and the acidic dissolution of this phase leading to silver ion release. By considering this, a complete set of equations is formulated describing oxygen and silver ion transport to and from particles' surfaces. These equations are solved in some limiting cases of nanoparticle dissolution in dilute suspensions. The obtained kinetic equations were used for the interpretation of experimental data pertinent to the dissolution kinetics of citrate-stabilized silver nanoparticles. In these kinetic measurements the role of pH and bulk suspension concentration was quantitatively evaluated by using the atomic absorption spectrometry (AAS). It was shown that the theoretical model adequately reflects the main features of the experimental results, especially the significant increase in the dissolution rate for lower pH. Also the presence of two kinetic regimes was quantitatively explained in terms of the decrease in the coverage of the fast dissolving oxide layer. The overall silver dissolution rate constants characterizing these two regimes were determined.

  6. Dissolution of ion exchange resin by hydrogen peroxide

    SciTech Connect

    Lee, S.C.

    1981-08-01

    The resin dissolution process was conducted successfully in full-scale equipment at the SRL Semiworks. A solution containing 0.001M Fe/sup 2 +/, or Fe/sup 3 +/, and 3 vol % H/sub 2/O/sub 2/ in 0.1M HNO/sub 3/ is sufficient to dissolve up to 40 vol % resin slurry (Dowex 50W-X8). Foaming and pressurization can be eliminated by maintaining the dissolution temperature below 99/sup 0/C. The recommended dissolution temperature range is 85 to 90/sup 0/C. Premixing hydrogen peroxide with all reactants will not create a safety hazard, but operating with a continual feed of hydrogen peroxide is recommended to control the dissolution rate. An air sparging rate of 1.0 to 1.5 scfm will provide sufficient mixing. Spent resin from chemical separation contains DTPA (diethylenetriaminepentaacetic acid) residue, and the resin must be washed with 0.1M NH/sub 4/ OH to remove excess DTPA before dissolution. Gamma irradiation of resin up to 4 kW-hr/L did not change the dissolution rate significantly.

  7. Observations of magnetite dissolution in poorly drained soils

    USGS Publications Warehouse

    Grimley, D.A.; Arruda, N.K.

    2007-01-01

    Dissolution of strongly magnetic minerals is a common and relatively rapid phenomenon in poorly drained soils of the central United States, resulting in low magnetic susceptibility (MS). Low Eh reducing conditions are primarily responsible for magnetic mineral dissolution; a process likely mediated by iron-reducing bacteria in the presence of soil organic matter. Based on transects across drainage sequences from nine sites, natural magnetic minerals (>5 ??m) extracted from surface soil consist of 54% ?? 18% magnetite, 21% ?? 11% titanomagnetite, and 17% ?? 14% ilmenite. Magnetite and titanomagnetite dissolution, assessed by scanning electron microscopy on a 0-to-3 scale, inversely correlates with surface soil MS (r = 0.53), a proxy for soil drainage at studied transects. Altered magnetite typically displays etch pits 5 ??m) include 26% ?? 18% anthropogenic fly ash that also exhibits greater dissolution in low MS soils (r = 0.38), indicating detectable alteration can occur within 150 years in low Eh soils. Laboratory induced reduction of magnetite, titanomagnetite, and magnetic fly ash, with a citrate-bicarbonate- dithionite solution, resulted in dissolution textures similar to those of in situ soil particles. Although experiments indicate that reductive dissolution of magnetite can occur abiotically under extreme conditions, bacteria likely play an important role in the natural environment. ?? 2007 Lippincott Williams & Wilkins, Inc.

  8. The depletion and regeneration of dissolution-active sites at the mineral-water interface: II. regeneration of active sites on α-Fe 2O 3 at pH 3 and pH 6

    NASA Astrophysics Data System (ADS)

    Samson, Sherry D.; Eggleston, Carrick M.

    2000-11-01

    Periods of transient nonsteady state dissolution can contain much information about dissolution mechanisms. Here, pH-jump-induced dissolution transients are used to explore the kinetics of production, at pH 3 and pH 6, of α-Fe 2O 3 surface sites active for dissolution at pH 1. We find that such sites are generated in a matter of minutes or less at higher pH. The steady state dissolution rate of hematite at pH 1 is ≤10.7 pmol m -2 s -1, whereas the rate of active site production at pH 6 in the first 30 min. of aging is at least 119 pmol m -2 s -1. Apparently, active sites are produced relatively slowly at low pH and relatively rapidly at circumneutral pH, despite the fact that dissolution rates are near a minimum at circumneutral pH. Using aqueous water exchange rates as a proxy for surface ligand exchange rates, this is qualitatively consistent with relatively slow water exchange by aqueous Fe 3+ ions at low pH and relatively rapid water exchange by Fe 3+ hydrolysis products (e.g., Fe(OH) 2+) at circumneutral pH. Consequently, the highest overall dissolution rates are achieved not at steady state at low pH, but by cycling between neutral and low pH. Our results call into question the assumption that oxide mineral surfaces, particularly those of iron and aluminum oxides, are inert on the time scale of proton or ligand adsorption (e.g., during the acid-base titrations typically used to measure oxide surface charge due to proton adsorption).

  9. Magnesite growth inhibition by organic ligands: An experimental study at 100, 120 and 146 °C

    NASA Astrophysics Data System (ADS)

    Gautier, Quentin; Bénézeth, Pascale; Schott, Jacques

    2016-05-01

    It has been proposed that simple organic ligands, which accelerate Mg-silicates dissolution, could be used to accelerate CO2 mineral sequestration through mineral carbonation. The influence of these ligands on magnesite growth has however never been quantified. In this work, we investigated the influence of three organic ligands: oxalate, citrate and EDTA on magnesite growth in alkaline conditions and at hydrothermal temperatures (100, 120 and 146 °C) using mixed flow reactors. We show that the studied carboxylates decrease magnesite growth rates, due to two converging mechanisms: Complexation of Mg2+ in solution, which decreases the saturation state of the solution. This effect was carefully taken into account by using a thermodynamic database relevant for the studied system. EDTA being the stronger chelate of the three investigated ligands, it has the strongest influence on solution saturation state. Adsorption of the ligand on magnesite surface growth sites, which decreases the kinetic rate constant of magnesite growth. We observed the following inhibition effectiveness of investigated organic ligands: citrate > EDTA > oxalate. While citrate exerts the strongest growth inhibition due to adsorption, it does not apparently lead to a complete interruption of magnesite growth. Preliminary adsorption experiments suggest that citrate adsorbs to active growth sites at the mineral surface with a much higher affinity than for the bulk of the surface. Using experimentally retrieved magnesite growth rate laws and published forsterite (Mg2SiO4) dissolution rate law, we performed simple numerical simulations to estimate the overall influence of the investigated ligands on the carbonation rates of forsterite. We observe that all ligands will clearly be detrimental to forsterite carbonation rates in typical conditions foreseen for Mg-silicates mineral carbonation. Their use may be positive for the carbonation of less reactive Mg-silicate minerals, but the delayed formation of

  10. The Effects of Freshwater Dissolution on Coral Geochemistry and Morphology

    NASA Astrophysics Data System (ADS)

    Wiggins, E. B.; Cobb, K. M.; Sayani, H. R.

    2012-12-01

    The aragonite skeletons of massive reef-building corals provide an invaluable high-resolution archive of past climate variability. However, studies have repeatedly shown that alteration of the coral skeleton (diagenesis), occurring as secondary cements and/or dissolution, is fairly prevalent among both modern and fossil corals. While the effects of secondary cements on bulk coral geochemistry and morphology have been extensively documented, the impacts of dissolution remain relatively unconstrained. Given that aragonite is metastable and that most fossil corals are exposed to rainfall for long periods, it follows that dissolution-related artifacts in fossil coral paleoclimate records merit further study. To date, the only study on coral dissolution suggests that dissolution does not significantly impact the oxygen isotopic ratios (δ18O), but leads to an increase of up to +0.06mmol/mol in coral Sr/Ca (equivalent to sea-surface temperature (SST) cooling artifacts of -1.2°C using standard Sr/Ca paleo-temperature conversions) [Hendy et.al., 2007]. Here we investigate the effects of freshwater dissolution on coral geochemistry and morphology by exposing a 2.5cm x 5cm segment of a modern coral from Palmyra Island (6°N, 162°W) to a constant freshwater drip for one week in order to simulate the effects of rainfall. Scanning electron microscope (SEM) images and coral δ18O and Sr/Ca measurements were taken before and after the coral was dissolved to assess the impacts of dissolution. We observe that dissolution occurs both on the surface and within the coral skeleton. Surface coral dissolution results in a "bumpy" surface, while interior dissolution targets centers of calcification. In the heavily-dissolved portions of the coral, nearly 60% of the skeleton surface is dissolved. In these areas δ18O shows a significant decrease of -0.2-0.4‰, which would correspond to an SST increase of +1-2°C in paleotemperature [Epstein, 1953]. Due to the relatively large range of Sr

  11. Mesoporous silica sub-micron spheres as drug dissolution enhancers: Influence of drug and matrix chemistry on functionality and stability.

    PubMed

    Brigo, Laura; Scomparin, Elisa; Galuppo, Marco; Capurso, Giovanni; Ferlin, Maria Grazia; Bello, Valentina; Realdon, Nicola; Brusatin, Giovanna; Morpurgo, Margherita

    2016-02-01

    Mesoporous silica particles prepared through a simplified Stöber method and low temperature solvent promoted surfactant removal are evaluated as dissolution enhancers for poorly soluble compounds, using a powerful anticancer agent belonging to pyrroloquinolinones as a model for anticancer oral therapy, and anti-inflammatory ibuprofen as a reference compound. Mesoporous powders composed of either pure silica or silica modified with aminopropyl residues are produced. The influence of material composition and drug chemical properties on drug loading capability and dissolution enhancement are studied. The two types of particles display similar size, surface area, porosity, erodibility, drug loading capability and stability. An up to 50% w/w drug loading is reached, showing correlation between drug concentration in adsorption medium and content in the final powder. Upon immersion in simulating body fluids, immediate drug dissolution occurred, allowing acceptor solutions to reach concentrations equal to or greater than drug saturation limits. The matrix composition influenced drug solution maximal concentration, complementing the dissolution enhancement generated by a mesoporous structure. This effect was found to depend on both matrix and drug chemical properties allowing us to hypothesise general prediction behaviour rules. PMID:26652411

  12. Mesoporous silica sub-micron spheres as drug dissolution enhancers: Influence of drug and matrix chemistry on functionality and stability.

    PubMed

    Brigo, Laura; Scomparin, Elisa; Galuppo, Marco; Capurso, Giovanni; Ferlin, Maria Grazia; Bello, Valentina; Realdon, Nicola; Brusatin, Giovanna; Morpurgo, Margherita

    2016-02-01

    Mesoporous silica particles prepared through a simplified Stöber method and low temperature solvent promoted surfactant removal are evaluated as dissolution enhancers for poorly soluble compounds, using a powerful anticancer agent belonging to pyrroloquinolinones as a model for anticancer oral therapy, and anti-inflammatory ibuprofen as a reference compound. Mesoporous powders composed of either pure silica or silica modified with aminopropyl residues are produced. The influence of material composition and drug chemical properties on drug loading capability and dissolution enhancement are studied. The two types of particles display similar size, surface area, porosity, erodibility, drug loading capability and stability. An up to 50% w/w drug loading is reached, showing correlation between drug concentration in adsorption medium and content in the final powder. Upon immersion in simulating body fluids, immediate drug dissolution occurred, allowing acceptor solutions to reach concentrations equal to or greater than drug saturation limits. The matrix composition influenced drug solution maximal concentration, complementing the dissolution enhancement generated by a mesoporous structure. This effect was found to depend on both matrix and drug chemical properties allowing us to hypothesise general prediction behaviour rules.

  13. Ligand Identification Scoring Algorithm (LISA)

    PubMed Central

    Zheng, Zheng; Merz, Kenneth M.

    2011-01-01

    A central problem in de novo drug design is determining the binding affinity of a ligand with a receptor. A new scoring algorithm is presented that estimates the binding affinity of a protein-ligand complex given a three-dimensional structure. The method, LISA (Ligand Identification Scoring Algorithm), uses an empirical scoring function to describe the binding free energy. Interaction terms have been designed to account for van der Waals (VDW) contacts, hydrogen bonding, desolvation effects and metal chelation to model the dissociation equilibrium constants using a linear model. Atom types have been introduced to differentiate the parameters for VDW, H-bonding interactions and metal chelation between different atom pairs. A training set of 492 protein-ligand complexes was selected for the fitting process. Different test sets have been examined to evaluate its ability to predict experimentally measured binding affinities. By comparing with other well known scoring functions, the results show that LISA has advantages over many existing scoring functions in simulating protein-ligand binding affinity, especially metalloprotein-ligand binding affinity. Artificial Neural Network (ANN) was also used in order to demonstrate that the energy terms in LISA are well designed and do not require extra cross terms. PMID:21561101

  14. Glass fiber dissolution in simulated lung fluid and measures needed to improve consistency and correspondence to in vivo dissolution.

    PubMed Central

    Mattson, S M

    1994-01-01

    The dissolution of a range of glass fibers including commercial glass and mineral wools has been studied using a modification of Gamble's solution in a flow system at pH 7.4 and 37 degrees C. Dissolution has been followed by weight loss, effluent analysis, and morphology change of fibers and bulk glass. Flow per glass surface area can strongly affect both dissolution rate and morphology due to the effect of the dissolution process on the fluid. Effluent pH is shown to be a guide for choice of optimum flow/area conditions. These conditions provide measurable concentrations of dissolved glass in the effluent while maintaining their concentrations below the point at which they significantly affect the dissolution process. SiO2 and Al2O3 vary widely in the extent to which they are involved in the leaching process, which removes alkalis, alkaline earths, and B2O3. This makes analysis of a single component in the effluent unsuitable as a means of comparing the dissolution rates of a wide range of compositions. PMID:7882963

  15. Development and evaluation of methods for starch dissolution using asymmetrical flow field-flow fractionation. Part II: Dissolution of amylose.

    PubMed

    Perez-Rea, Daysi; Bergenståhl, Björn; Nilsson, Lars

    2016-02-01

    In this paper, we investigate whether dissolution in water under autoclaving conditions (140 °C, 20 min) or in dimethyl sulfoxide, DMSO (100 °C, 1 h), is preferable for characterization of amylose. Two types of amylose, potato and maize, were dissolved either in water using an autoclave or in DMSO. On the aqueous solutions obtained, the extent of molecular dissolution of the sample (referred to as the dissolution yield) was determined by enzymatic analysis as well as the molecular properties, such as molar mass and root-mean-square radius, obtained with asymmetrical flow field-flow fractionation coupled to multi-angle light scattering and differential refractive index detection (AF4-MALS-dRI). The results showed that both dissolution methods are efficient at dissolving amylose. However, AF4-MALS-dRI analysis revealed substantial differences. Amylose aqueous solutions obtained by dissolution in DMSO were relatively stable over time, but the dissolution method in autoclave caused some degradation of the molecules, and their solutions display a high tendency to retrograde. PMID:26232931

  16. Dissolution in Fractured and Porous Rocks - the Cave Formation Paradox and Other Instabilities

    NASA Astrophysics Data System (ADS)

    Szymczak, P.; Ladd, A. J. C.

    2012-04-01

    It has long been realized that limestone caves are solutional in origin; the carbonic acid-enriched groundwater forms a weakly acidic solution which dissolves the surrounding limestone as it percolates through the fracture network. Under the simplest assumptions - uniform flow and linear kinetics - the concentration of reactant decays exponentially with distance into the fracture, making it apparently impossible for long conduits to develop. How does the dissolution get so deep then? The answer until recently has been described in terms of changes in chemical kinetics: in natural calcite the reaction rate decreases by orders of magnitude near saturation, which gives a slightly undersaturated solution possibility to penetrate deeper into the fractured rock. Although this is an appealing and widely accepted resolution of the cave formation paradox, it turns out to be incomplete. Both the computer simulations [1] and laboratory experiments [2] show that a fracture does not necessarily open uniformly across its width, but can develop localized regions of dissolution. We show that there is in fact a universal instability in the equations for fracture dissolution [3], even under the most idealized circumstances: i.e. a fracture modeled as two parallel plates, laminar flow, and linear reaction kinetics at the fracture surfaces. This generic instability provides a more effective means to promote dissolution than changes in chemical kinetics and has a profound effect on how long it takes for breakthrough (when the fracture opens along its whole length) to occur. This instability is related to a similar phenomenon in the reactive flow in porous rocks, first described by Chadam et. al [4] (so-called reactive-infiltration instability). The physical nature of both instabilites is different: the former is associated with an initial, uniform porosity state and the other with a steadily propagating dissolution front that separates regions of high and low porosity. We discuss the

  17. NKG2D ligands mediate immunosurveillance of senescent cells.

    PubMed

    Sagiv, Adi; Burton, Dominick G A; Moshayev, Zhana; Vadai, Ezra; Wensveen, Felix; Ben-Dor, Shifra; Golani, Ofra; Polic, Bojan; Krizhanovsky, Valery

    2016-02-01

    Cellular senescence is a stress response mechanism that limits tumorigenesis and tissue damage. Induction of cellular senescence commonly coincides with an immunogenic phenotype that promotes self-elimination by components of the immune system, thereby facilitating tumor suppression and limiting excess fibrosis during wound repair. The mechanisms by which senescent cells regulate their immune surveillance are not completely understood. Here we show that ligands of an activating Natural Killer (NK) cell receptor (NKG2D), MICA and ULBP2 are consistently up-regulated following induction of replicative senescence, oncogene-induced senescence and DNA damage - induced senescence. MICA and ULBP2 proteins are necessary for efficient NK-mediated cytotoxicity towards senescent fibroblasts. The mechanisms regulating the initial expression of NKG2D ligands in senescent cells are dependent on a DNA damage response, whilst continuous expression of these ligands is regulated by the ERK signaling pathway. In liver fibrosis, the accumulation of senescent activated stellate cells is increased in mice lacking NKG2D receptor leading to increased fibrosis. Overall, our results provide new insights into the mechanisms regulating the expression of immune ligands in senescent cells and reveal the importance of NKG2D receptor-ligand interaction in protecting against liver fibrosis. PMID:26878797

  18. In vitro dissolution of uranium oxide by baboon alveolar macrophages.

    PubMed Central

    Poncy, J L; Metivier, H; Dhilly, M; Verry, M; Masse, R

    1992-01-01

    In vitro cellular dissolution tests for insoluble forms of uranium oxide are technically difficult with conventional methodology using adherent alveolar macrophages. The limited number of cells per flask and the slow dissolution rate in a large volume of nutritive medium are obvious restricting factors. Macrophages in suspension cannot be substituted because they represent different and poorly reproducible functional subtypes with regard to activation and enzyme secretion. Preliminary results on the dissolution of uranium oxide using immobilized alveolar macrophages are promising because large numbers of highly functional macrophages can be cultured in a limited volume. Cells were obtained by bronchoalveolar lavages performed on baboons (Papio papio) and then immobilized after the phagocytosis of uranium octoxide (U3O8) particles in alginate beads linked with Ca2+. The dissolution rate expressed as percentage of initial uranium content in cells was 0.039 +/- 0.016%/day for particles with a count median geometric diameter of 3.84 microns(sigma g = 1.84). A 2-fold increase in the dissolution rate was observed when the same number of particles was immobilized without macrophages. These results, obtained in vitro, suggest that the U3O8 preparation investigated should be assigned to inhalation class Y as recommended by the International Commission on Radiological Protection. Future experiments are intended to clarify this preliminary work and to examine the dissolution characteristics of other particles such as uranium dioxide. It is recommended that the dissolution rate should be measured over an interval of 3 weeks, which is compatible with the survival time of immobilized cells in culture and may reveal transformation states occurring with aging of the particles. PMID:1396447

  19. Controlled evaluation of silver nanoparticle dissolution using atomic force microscopy.

    PubMed

    Kent, Ronald D; Vikesland, Peter J

    2012-07-01

    Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7.0, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, the in-plane radius decreased by 5-11 nm, and the height increased by 6-12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10-550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of unaggregated AgNP dissolution. PMID:22191460

  20. Simulation of in vitro dissolution behavior using DDDPlus™.

    PubMed

    Almukainzi, May; Okumu, Arthur; Wei, Hai; Löbenberg, Raimar

    2015-02-01

    Dissolution testing is a performance test for many dosage forms including tablets and capsules. The objective of this study was to evaluate if computer simulations can predict the in vitro dissolution of two model drugs for which different dissolution data were available. Published montelukast sodium and glyburide dissolution data was used for the simulations. Different pharmacopeial and biorelevant buffers, volumes, and rotations speeds were evaluated. Additionally, a pH change protocol was evaluated using these buffers. DDDPlus™ 3, Beta version (Simulation Plus, Inc.), was used to simulate the in vitro dissolution data. The simulated data were compared with the in vitro data. A regression coefficient between predicted and observed data was used to assess the simulations. The statistical analysis of Montelukast sodium showed that there was a significant correlation between the in vitro release data and the predicted data for all cases except for one buffer. For glyburide, there was also a significant correlation between the experimental data and the predicted data using single pH conditions. Using the dynamic pH protocol, a correlation was significant for one biorelevant media. The simulations showed that both in vitro drug releases were sensitive to solubility effects which confirmed their BCS class II category. Computer simulations of the in vitro release using DDDPlus™ have the potential to estimate the in vivo dissolution at an early stage in the drug development process. This might be used to choose the most appropriate dissolution condition to establish IVIVC and to develop biorelevant in vitro performance tests to capture critical product attributes for quality control procedures in quality by design environments. PMID:25409918

  1. In vitro dissolution of uranium oxide by baboon alveolar macrophages

    SciTech Connect

    Poncy, J.L.; Dhilly, M.; Verry, M. ); Metivier, H. ); Masse, R. )

    1992-07-01

    In vitro cellular dissolution tests for insoluble forms of uranium oxide are technically difficult with conventional methodology using adherent alveolar macrophages. The limited number of cells per flask and the slow dissolution rate in a large volume of nutritive medium are obvious restricting factors. macrophages in suspension cannot be substituted because they represent different and poorly reproducible functional subtypes with regard to activation and enzyme secretion. Preliminary results on the dissolution of uranium oxide using immobilized alveolar macrophages are promising because large numbers of highly function macrophages can be cultured in a limited volume. Cells were obtained by bronchoalveolar lavages performed on baboons (Papio papio) and then immobilized after the phagocytosis of uranium octoxide (U[sub 3]O[sub 8]) particles in alginate beads linked with Ca[sup 2+]. The dissolution rate expressed as percentage of initial uranium content in cells was 0.039 [+-] 0.016%/day for particles with a count median geometric diameter of 3.84 [mu]m([sigma][sub g] = 1.84). A 2-fold increase in the dissolution rate was observed when the same number of particles was immobilized without macrophages. These results, obtained in vitro, suggest that the U[sub 3]O[sub g] preparation investigated should be assigned to inhalation class Y as recommended by the International Commission on Radiological Protection. Future experiments are intended to clarify this preliminary work and to examine the dissolution characteristics of other particles such as uranium dioxide. It is recommended that the dissolution rate should be measured over an interval of 3 weeks, which is compatible with the survival time of immobilized cells in culture and may reveal transformation states occurring with aging of the particles. 23 refs., 3 figs.

  2. Controlled evaluation of silver nanoparticle dissolution using atomic force microscopy.

    PubMed

    Kent, Ronald D; Vikesland, Peter J

    2012-07-01

    Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7.0, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, the in-plane radius decreased by 5-11 nm, and the height increased by 6-12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10-550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of unaggregated AgNP dissolution.

  3. Effect of diffusive transport limitations on UO2 dissolution.

    PubMed

    Giammar, Daniel E; Cerrato, José M; Mehta, Vrajesh; Wang, Zimeng; Wang, Yin; Pepping, Troy J; Ulrich, Kai-Uwe; Lezama-Pacheco, Juan S; Bargar, John R

    2012-11-15

    The effects of diffusive transport limitations on the dissolution of UO(2) were investigated using an artificial groundwater prepared to simulate the conditions at the Old Rifle aquifer site in Colorado, USA. Controlled batch, continuously-stirred tank (CSTR), and plug flow reactors were used to study UO(2) dissolution in the absence and presence of diffusive limitations exerted by permeable sample cells. The net rate of uranium release following oxidative UO(2) dissolution obtained from diffusion-limited batch experiments was ten times lower than that obtained for UO(2) dissolution with no permeable sample cells. The release rate of uranium to bulk solution from UO(2) contained in permeable sample cells under advective flow conditions was more than 100 times lower than that obtained from CSTR experiments without diffusive limitations. A 1-dimensional transport model was developed that could successfully simulate diffusion-limited release of U following oxidative UO(2) dissolution with the dominant rate-limiting process being the transport of U(VI) out of the cells. Scanning electron microscopy, X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS) characterization of the UO(2) solids recovered from batch experiments suggest that oxidative dissolution was more evident in the absence of diffusive limitations. Ca-EXAFS spectra indicate the presence of Ca in the reacted UO(2) solids with a coordination environment similar to that of a Ca-O-Si mineral. The findings from this study advance our overall understanding of the coupling of geochemical and transport processes that can lead to differences in dissolution rates measured in the field and in laboratory experiments.

  4. Effect of synovial fluid, phosphate-buffered saline solution, and water on the dissolution and corrosion properties of CoCrMo alloys as used in orthopedic implants.

    PubMed

    Lewis, A C; Kilburn, M R; Papageorgiou, I; Allen, G C; Case, C P

    2005-06-15

    The corrosion and dissolution of high- and low-carbon CoCrMo alloys, as used in orthopedic joint replacements, were studied by immersing samples in phosphate-buffered saline (PBS), water, and synovial fluid at 37 degrees C for up to 35 days. Bulk properties were analyzed with a fine ion beam microscope. Surface analyses by X-ray photoelectron spectroscopy and Auger electron spectroscopy showed surprisingly that synovial fluid produced a thin oxide/hydroxide layer. Release of ions into solution from the alloy also followed an unexpected pattern where synovial fluid, of all the samples, had the highest Cr concentration but the lowest Co concentration. The presence of carbide inclusions in the alloy did not affect the corrosion or the dissolution mechanisms, although the carbides were a significant feature on the metal surface. Only one mechanism was recognized as controlling the thickness of the oxide/hydroxide interface. The analysis of the dissolved metal showed two mechanisms at work: (1) a protein film caused ligand-induced dissolution, increasing the Cr concentration in synovial fluid, and was explained by the equilibrium constants; (2) corrosion at the interface increased the Co in PBS. The effect of prepassivating the samples (ASTM F-86-01) did not always have the desired effect of reducing dissolution. The release of Cr into PBS increased after prepassivation. The metal-synovial fluid interface did not contain calcium phosphate as a deposit, typically found where samples are exposed to calcium rich bodily fluids.

  5. Another step toward DNA selective targeting: NiII and CuII complexes of a Schiff base ligand able to bind gene promoter G-quadruplexes† †Electronic supplementary information (ESI) available. CCDC 1451694–1451696. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6dt00648e Click here for additional data file. Click here for additional data file.

    PubMed Central

    Lötsch, Daniela; van Schoonhoven, Sushilla; Roller, Alexander; Kowol, Christian R.; Berger, Walter; Keppler, Bernhard K.

    2016-01-01

    DNA G-rich sequences are able to form four-stranded structures organized in stacked guanine tetrads. These structures, called G-quadruplexes, were found to have an important role in the regulation of oncogenes expression and became, for such a reason, appealing targets for anticancer drugs. Aiming at finding selective G-quadruplex binders, we have designed, synthesized and characterized a new water soluble Salen-like Schiff base ligand and its NiII and CuII metal complexes. UV-Vis, circular dichroism and FRET measurements indicated that the nickel complex can stabilize oncogene promoter G-quadruplexes with high selectivity, presenting no interactions with duplex DNA at all. The same compound exhibited dose-dependent cytotoxic activity in MCF-7 breast cancer cells when combined with lipofectamine as lipophilic carrier. PMID:27054617

  6. Effect of solution saturation state and temperature on diopside dissolution

    SciTech Connect

    Dixit, S; Carroll, S A

    2007-03-23

    Steady-state dissolution rates of diopside are measured as a function of solution saturation state using a titanium flow-through reactor at pH 7.5 and temperature ranging from 125 to 175 C. Diopside dissolved stoichiometrically under all experimental conditions and rates were not dependent on sample history. At each temperature, rates continuously decreased by two orders of magnitude as equilibrium was approached and did not exhibit a dissolution plateau of constant rates at high degrees of undersaturation. The variation of diopside dissolution rates with solution saturation can be described equally well with a ion exchange model based on transition state theory or pit nucleation model based on crystal growth/dissolution theory from 125 to 175 C. At 175 C, both models over predict dissolution rates by two orders of magnitude indicating that a secondary phase precipitated in the experiments. The ion exchange model assumes the formation of a Si-rich, Mg-deficient precursor complex. Lack of dependence of rates on steady-state aqueous calcium concentration supports the formation of such a complex, which is formed by exchange of protons for magnesium ions at the surface.

  7. Dissolution Enhancement of Rosuvastatin Calcium by Liquisolid Compact Technique

    PubMed Central

    Kapure, V. J.; Pande, V. V.; Deshmukh, P. K.

    2013-01-01

    In present investigation liquisolid compact technique is investigated as a tool for enhanced dissolution of poorly water-soluble drug Rosuvastatin calcium (RVT). The model drug RVT, a HMG-Co A reductase inhibitor was formulated in form of directly compressed tablets and liquisolid compacts; and studied for in-vitro release characteristics at different dissolution conditions. In this technique, liquid medications of water insoluble drugs in non-volatile liquid vehicles can be converted into acceptably flowing and compressible powders. Formulated systems were assessed for precompression parameters like flow properties of liquisolid system, Fourior transform infra red spectra (FTIR) analysis, X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC), and post compression parameters like content uniformity, weight variation, hardness and friability, disintegration test, wetting time, in vitro dissolution studies, effect of dissolution volume on drug release rate, and estimation of fraction of molecularly dispersed drug in liquid medication. As liquisolid compacts demonstrated significantly higher drug release rates, we lead to conclusion that it could be a promising strategy in improving the dissolution of poor water soluble drugs and formulating immediate release solid dosage forms. PMID:26555972

  8. Monitoring crystal dissolution at nanometer resolution using laser reflectometry

    NASA Astrophysics Data System (ADS)

    Eggington, P. J.; Taylor, A. G.

    2000-01-01

    Laser reflectometry has been used for the first time as an in situ real-time monitor of the dissolution of the (0 0 1) face of KClO 3 crystals into aqueous solution. During the dissolution process the reflected light was subject to constructive and destructive interference caused by the movement of crystal boundaries. This produced Fabry-Perot oscillations similar to the widely exploited phenomenon used in the laser reflectometry-based metrology of semiconductor surfaces. The method is adapted and theoretical fits to the observed data are presented. The quality of the data allows dissolution rates of 100 nm s -1 to be measured accurately. Data gained by this method was used to verify the concentration dependence of the dissolution rate and confirm it as a diffusion-controlled mechanism. The hydrodynamic radius of the diffusing ions was found to be 0.224 nm, in agreement with literature values. The potential of laser reflectometry for use as an effective probe sensitive to changes in crystal surface morphology during dissolution has also been demonstrated.

  9. Three-stage sequential statistical dissolution testing rules.

    PubMed

    Tsong, Yi; Shen, Meiyu; Shah, Vinod P

    2004-08-01

    The U.S. Pharmacopoeia (USP) general monograph provides a standard for dissolution compliance with the requirements as stated in the individual USP monograph for a tablet or capsule dosage form. The USP monograph sets performance limit on dissolution in terms of a specific percentage Q that the drug product is required to be dissolved at a specified time. Japan Pharmacopoeia provides acceptance rules different from USP. However the objective of the acceptance rules was not defined in terms of the inference of the whole lot by either USP, European Pharmacopoeia (EP) or Japan Pharmacopoeia (JP). The operating characteristics' curves of these rules are all shown to be sensitive to the true mean dissolution and do not reject a lot which has a large percentage of tablets that dissolve with less than the specified limit Q. This is especially true when the mean dissolution is close to the specification value. We proposed that the goal of the dissolution test sampling plan is to accept a lot at least 90% of the tablets dissolved more than a pre-specified amount Q at the specific time. The group sequential procedure derived accordingly is shown to outperform both USP and JP in controlling the type I error rate under normality assumption.

  10. How good is cola for dissolution of gastric phytobezoars?

    PubMed Central

    Lee, Beom Jae; Park, Jong-Jae; Chun, Hoon Jai; Kim, Ji Hoon; Yeon, Jong Eun; Jeen, Yoon Tae; Kim, Jae Seon; Byun, Kwan Soo; Lee, Sang Woo; Choi, Jae Hyun; Kim, Chang Duck; Ryu, Ho Sang; Bak, Young-Tae

    2009-01-01

    AIM: To evaluate the efficacy of cola treatment for gastric phytobezoars, including diospyrobezoars. METHODS: A total of 17 patients (range: 48 to 78 years) with symptomatic gastric phytobezoars treated with cola and adjuvant endoscopic therapy were reviewed. Three liters of cola lavage (10 cases) or drink (7 cases) were initially used, and then endoscopic fragmentation was done for the remnant bezoars by using a lithotripsy basket or a polypectomy snare. The overall success of dissolving a gastric phytobezoars with using three liters of cola and the clinical and endoscopic findings were compared retrospectively between four cases of complete dissolution by using only cola and 13 cases of partial dissolution with cola. RESULTS: After 3 L of cola lavage or drinking, a complete dissolution of bezoars was achieved in four patients (23.5%), while 13 cases (76.5%) were only partially dissolved. Phytobezoars (4 of 6 cases) were observed more frequently than diospyrobezoars (0 of 11) in the group that underwent complete dissolution (P = 0.006). Gender, symptom duration, size of bezoar and method of cola administration were not significantly different between the two groups. Twelve of 13 patients with residual bezoars were completely treated with a combination of cola and endoscopic fragmentation. CONCLUSION: The rate of complete dissolution with three liters of cola was 23.5%, but no case of diospyrobezoar was completely dissolved using this method. However, pretreatment with cola may be helpful and facilitate endoscopic fragmentation of gastric phytobezoars. PMID:19437568

  11. On the effects of subsurface parameters on evaporite dissolution (Switzerland).

    PubMed

    Zidane, Ali; Zechner, Eric; Huggenberger, Peter; Younes, Anis

    2014-05-01

    Uncontrolled subsurface evaporite dissolution could lead to hazards such as land subsidence. Observed subsidences in a study area of Northwestern Switzerland were mainly due to subsurface dissolution (subrosion) of evaporites such as halite and gypsum. A set of 2D density driven flow simulations were evaluated along 1000 m long and 150 m deep 2D cross sections within the study area that is characterized by tectonic horst and graben structures. The simulations were conducted to study the effect of the different subsurface parameters that could affect the dissolution process. The heterogeneity of normal faults and its impact on the dissolution of evaporites is studied by considering several permeable faults that include non-permeable areas. The mixed finite element method (MFE) is used to solve the flow equation, coupled with the multipoint flux approximation (MPFA) and the discontinuous Galerkin method (DG) to solve the diffusion and the advection parts of the transport equation. Results show that the number of faults above the lower aquifer that contains the salt layer is considered as the most important factor that affects the dissolution compared to the other investigated parameters of thickness of the zone above the halite formation, a dynamic conductivity of the lower aquifer, and varying boundary conditions in the upper aquifer. PMID:24650646

  12. Dissolution of magnetically marked tablets: investigations in a physical phantom.

    PubMed

    Biller, S; Domey, J; Fiedler, P; Holzhey, R; Richert, H; Haueisen, J

    2012-01-01

    Pharmacological research is strongly driven by maximizing the bioavailability of new pharmaceuticals. For orally applied drugs the bioavailability highly depends on the process of dissolution in the gastrointestinal tract and is affected by numerous physiological and environmental factors. Available techniques for in vivo monitoring of the dissolution process are very limited and not applicable for large studies. The technique of magnetic marker monitoring provides new prospects for these investigations. However, it is currently limited due to low fields common magnetic markers produce. Hence, only highly sensitive sensors are applicable. In this paper, we performed dissolution tests of novel markers in a physical phantom with magnetoresistive sensors in an unshielded environment. The markers were continuously localized and the movement through the phantom was tracked. By analyzing the changing magnetic moment of the markers we were able to monitor the progress of dissolution in the phantom. We conclude that our proposed phantom and tracking technique is an important step towards new systems for in vivo monitoring of pharmaceutical dissolution processes. PMID:23366328

  13. Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

    NASA Astrophysics Data System (ADS)

    Antia, A. N.; Suffrian, K.; Holste, L.; Müller, M. N.; Nejstgaard, J. C.; Simonelli, P.; Carotenuto, Y.; Putzeys, S.

    2008-01-01

    Independent of the ongoing acidification of surface seawater, the majority of the calcium carbonate produced in the pelagial is dissolved by natural processes above the lysocline. We investigate to what extent grazing and passage of coccolithophorids through the guts of copepods and the food vacuoles of microzooplankton contribute to calcite dissolution. In laboratory experiments where the coccolithophorid Emiliania huxleyi was fed to the rotifer Brachionus plicatilis, the heterotrophic flagellate Oxyrrhis marina and the copepod Acartia tonsa, calcite dissolution rates of 45-55%, 37-53% and 5-22% of ingested calcite were found. We ascribe higher loss rates in microzooplankton food vacuoles as compared to copepod guts to the strongly acidic digestion and the individual packaging of algal cells. In further experiments, specific rates of calcification and calcite dissolution were also measured in natural populations during the PeECE III mesocosm study under differing ambient pCO2 concentrations. Microzooplankton grazing accounted for between 27 and 70% of the dynamic calcite stock being lost per day, with no measurable effect of CO2 treatment. These measured calcite dissolution rates indicate that dissolution of calcite in the guts of microzooplankton and copepods can account for the calcite losses calculated for the global ocean using budget and model estimates.

  14. On the effects of subsurface parameters on evaporite dissolution (Switzerland).

    PubMed

    Zidane, Ali; Zechner, Eric; Huggenberger, Peter; Younes, Anis

    2014-05-01

    Uncontrolled subsurface evaporite dissolution could lead to hazards such as land subsidence. Observed subsidences in a study area of Northwestern Switzerland were mainly due to subsurface dissolution (subrosion) of evaporites such as halite and gypsum. A set of 2D density driven flow simulations were evaluated along 1000 m long and 150 m deep 2D cross sections within the study area that is characterized by tectonic horst and graben structures. The simulations were conducted to study the effect of the different subsurface parameters that could affect the dissolution process. The heterogeneity of normal faults and its impact on the dissolution of evaporites is studied by considering several permeable faults that include non-permeable areas. The mixed finite element method (MFE) is used to solve the flow equation, coupled with the multipoint flux approximation (MPFA) and the discontinuous Galerkin method (DG) to solve the diffusion and the advection parts of the transport equation. Results show that the number of faults above the lower aquifer that contains the salt layer is considered as the most important factor that affects the dissolution compared to the other investigated parameters of thickness of the zone above the halite formation, a dynamic conductivity of the lower aquifer, and varying boundary conditions in the upper aquifer.

  15. Combinatorial localized dissolution analysis: Application to acid-induced dissolution of dental enamel and the effect of surface treatments.

    PubMed

    Parker, Alexander S; Al Botros, Rehab; Kinnear, Sophie L; Snowden, Michael E; McKelvey, Kim; Ashcroft, Alexander T; Carvell, Mel; Joiner, Andrew; Peruffo, Massimo; Philpotts, Carol; Unwin, Patrick R

    2016-08-15

    A combination of scanning electrochemical cell microscopy (SECCM) and atomic force microscopy (AFM) is used to quantitatively study the acid-induced dissolution of dental enamel. A micron-scale liquid meniscus formed at the end of a dual barrelled pipette, which constitutes the SECCM probe, is brought into contact with the enamel surface for a defined period. Dissolution occurs at the interface of the meniscus and the enamel surface, under conditions of well-defined mass transport, creating etch pits that are then analysed via AFM. This technique is applied to bovine dental enamel, and the effect of various treatments of the enamel surface on acid dissolution (1mM HNO3) is studied. The treatments investigated are zinc ions, fluoride ions and the two combined. A finite element method (FEM) simulation of SECCM mass transport and interfacial reactivity, allows the intrinsic rate constant for acid-induced dissolution to be quantitatively determined. The dissolution of enamel, in terms of Ca(2+) flux ( [Formula: see text] ), is first order with respect to the interfacial proton concentration and given by the following rate law: [Formula: see text] , with k0=0.099±0.008cms(-1). Treating the enamel with either fluoride or zinc ions slows the dissolution rate, although in this model system the partly protective barrier only extends around 10-20nm into the enamel surface, so that after a period of a few seconds dissolution of modified surfaces tends towards that of native enamel. A combination of both treatments exhibits the greatest protection to the enamel surface, but the effect is again transient.

  16. Combinatorial localized dissolution analysis: Application to acid-induced dissolution of dental enamel and the effect of surface treatments.

    PubMed

    Parker, Alexander S; Al Botros, Rehab; Kinnear, Sophie L; Snowden, Michael E; McKelvey, Kim; Ashcroft, Alexander T; Carvell, Mel; Joiner, Andrew; Peruffo, Massimo; Philpotts, Carol; Unwin, Patrick R

    2016-08-15

    A combination of scanning electrochemical cell microscopy (SECCM) and atomic force microscopy (AFM) is used to quantitatively study the acid-induced dissolution of dental enamel. A micron-scale liquid meniscus formed at the end of a dual barrelled pipette, which constitutes the SECCM probe, is brought into contact with the enamel surface for a defined period. Dissolution occurs at the interface of the meniscus and the enamel surface, under conditions of well-defined mass transport, creating etch pits that are then analysed via AFM. This technique is applied to bovine dental enamel, and the effect of various treatments of the enamel surface on acid dissolution (1mM HNO3) is studied. The treatments investigated are zinc ions, fluoride ions and the two combined. A finite element method (FEM) simulation of SECCM mass transport and interfacial reactivity, allows the intrinsic rate constant for acid-induced dissolution to be quantitatively determined. The dissolution of enamel, in terms of Ca(2+) flux ( [Formula: see text] ), is first order with respect to the interfacial proton concentration and given by the following rate law: [Formula: see text] , with k0=0.099±0.008cms(-1). Treating the enamel with either fluoride or zinc ions slows the dissolution rate, although in this model system the partly protective barrier only extends around 10-20nm into the enamel surface, so that after a period of a few seconds dissolution of modified surfaces tends towards that of native enamel. A combination of both treatments exhibits the greatest protection to the enamel surface, but the effect is again transient. PMID:27209395

  17. Designing ligands to bind proteins.

    PubMed

    Whitesides, George M; Krishnamurthy, Vijay M

    2005-11-01

    The ability to design drugs (so-called 'rational drug design') has been one of the long-term objectives of chemistry for 50 years. It is an exceptionally difficult problem, and many of its parts lie outside the expertise of chemistry. The much more limited problem - how to design tight-binding ligands (rational ligand design) - would seem to be one that chemistry could solve, but has also proved remarkably recalcitrant. The question is 'Why is it so difficult?' and the answer is 'We still don't entirely know'. This perspective discusses some of the technical issues - potential functions, protein plasticity, enthalpy/entropy compensation, and others - that contribute, and suggests areas where fundamental understanding of protein-ligand interactions falls short of what is needed. It surveys recent technological developments (in particular, isothermal titration calorimetry) that will, hopefully, make now the time for serious progress in this area. It concludes with the calorimetric examination of the association of a series of systematically varied ligands with a model protein. The counterintuitive thermodynamic results observed serve to illustrate that, even in relatively simple systems, understanding protein-ligand association is challenging.

  18. High Level Waste System Impacts from Acid Dissolution of Sludge

    SciTech Connect

    KETUSKY, EDWARD

    2006-04-20

    This research evaluates the ability of OLI{copyright} equilibrium based software to forecast Savannah River Site High Level Waste system impacts from oxalic acid dissolution of Tank 1-15 sludge heels. Without further laboratory and field testing, only the use of oxalic acid can be considered plausible to support sludge heel dissolution on multiple tanks. Using OLI{copyright} and available test results, a dissolution model is constructed and validated. Material and energy balances, coupled with the model, identify potential safety concerns. Overpressurization and overheating are shown to be unlikely. Corrosion induced hydrogen could, however, overwhelm the tank ventilation. While pH adjustment can restore the minimal hydrogen generation, resultant precipitates will notably increase the sludge volume. OLI{copyright} is used to develop a flowsheet such that additional sludge vitrification canisters and other negative system impacts are minimized. Sensitivity analyses are used to assess the processability impacts from variations in the sludge/quantities of acids.

  19. Glass Dissolution: Testing and Modeling for Long-Term Behavior.

    SciTech Connect

    Strachan, Denis M. )

    2001-09-01

    The basic concepts of thermodynamics and kinetics are discussed in relationship to glass dissolution testing. While it seems like these subjects are too basic to be discussed in a journal article, it is often the case that we forget these concepts when planning and designing dissolution tests and interpreting the results that come from these tests. The possible connection between the composition of the dissolving glass and its long-term behavior is discussed. Results from a preliminary study suggest that the aluminum content of a glass is important to its long-term behavior. The formation of a zeolite can cause the glass dissolution rate to increase under certain conditions that can be modeled. Results indicate that complex glasses can be modeled with a glass containing as little as six components.

  20. Progressive dissolution of titanomagnetites at ODP Site 653 (Tyrrhenian Sea)

    NASA Astrophysics Data System (ADS)

    Channell, J. E. T.; Hawthorne, T.

    1990-01-01

    Magnetic properties, microscopy and ferrous/ferric iron ratio document increasing down-core alteration of titanomagnetite to iron sulfide at ODP Site 653 (Leg 107, Tyrrhenian Sea). Changes in magnetic properties are interpreted to indicate a grain size increase in titanomagnetite to 40 m below seafloor (bsf) and a grain size decrease from this level to about 150 m bsf, as dissolution affects first the fine grained and then the coarser grained magnetite. The availability of dissolved sulfate from underlying Messinian evaporites may account for the sulfide supply at depth and hence for the prolonged dissolution process. Dissolution at Leg 107 sites adjacent to Site 653 is less pronounced, possibly by the availability of organic matter that can be metabolised by sulfate-reducing bacteria.

  1. Interactions between ciprofloxacin and antacids--dissolution and adsorption studies.

    PubMed

    Arayne, M Saeed; Sultana, Najma; Hussain, Fida

    2005-01-01

    Ciprofloxacin is a fluorinated quinolone antibacterial agent extensively used against both Gram-positive and Gram-negative microorganisms. In certain polytherapy programs, ciprofloxacin can be administered with some antacids that could modify its dissolution rate and reduce its absorption leading to therapeutic failure. The aim of this study was to evaluate the influence of some antacids on the availability of ciprofloxacin. The release of ciprofloxacin from tablets in the presence of antacids, such as sodium bicarbonate, calcium hydroxide, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, magnesium trisilicate and magaldrate was studied on BP 2002 dissolution test apparatus. These studies were carried out in simulated gastric and intestinal juices for 3 hours at 37 degrees C. The results confirmed that the dissolution rate of tablets was markedly retarded in the presence of all the antacids studied. Magaldrate and calcium carbonate in simulated gastric juice exhibited relatively higher adsorption capacities, as did magnesium trisilicate and calcium hydroxide in simulated intestinal juice.

  2. Dissolution control of Mg by cellulose acetate-polyelectrolyte membranes.

    PubMed

    Yliniemi, Kirsi; Wilson, Benjamin P; Singer, Ferdinand; Höhn, Sarah; Kontturi, Eero; Virtanen, Sannakaisa

    2014-12-24

    Cellulose acetate (CA)-based membranes are used for Mg dissolution control: the permeability of the membrane is adjusted by additions of the polyelectrolyte, poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA). Spin-coated films were characterized with FT-IR, and once exposed to an aqueous solution the film distends and starts acting as a membrane which controls the flow of ions and H2 gas. Electrochemical measurements (linear sweep voltammograms, open-circuit potential, and polarization) show that by altering the CA:PDMAEMA ratio the dissolution rate of Mg can be controlled. Such a control over Mg dissolution is crucial if Mg is to be considered as a viable, temporary biomedical implant material. Furthermore, the accumulation of corrosion products between the membrane and the sample diminishes the undesirable effects of high local pH and H2 formation which takes place during the corrosion process.

  3. The dissolution of calcium oxalate kidney stones. A kinetic study.

    PubMed

    Tomazic, B B; Nancollas, G H

    1982-07-01

    The rates of dissolution of calcium oxalate monohydrate (COM) and dihydrate (COD) and of kidney stones containing these phases has been studied in 0.15 M sodium chloride solution at 37C. In contrast to the diffusion controlled dissolution of the pure synthetic phases, the kidney stones appear to dissolve considerably more slowly by a predominantly surface controlled process, independent of fluid dynamics. The differences between the dissolution rates of the synthetic and stone minerals become greater as the reactions approach equilibrium. As was found for the COD mineral, the dihydrate stone material transforms into the thermodynamically more stable monohydrate phase. The COD stone phase is significantly stabilized in the presence of inhibitors such as polyphosphate and magnesium ions. This may be an important factor in explaining the observed presence of dihydrate as a surface phase in many reported cases of calcium oxalate lithiasis.

  4. Dissolution of a Colloidal Particle in an Oscillatory Fluid Medium

    NASA Astrophysics Data System (ADS)

    Ye, Dezhuang; Li, Ji-Qin; Bogner, Robin; Fan, Tai-Hsi

    Understanding dissolution kinetics of a colloidal particle in an aqueous solution is of great importance in many pharmaceutical and biochemical applications. We present theoretical analysis of low Reynolds number transient dynamics and mass transfer of a dissolving spherical particle in a unidirectional oscillatory flow. The coupling of fluid flow and passive motion of the particle are resolved analytically, and the transient mass transfer associated with the oscillation of the particle is numerically computed. The flow patterns, diffusive and convective transport phenomena, and the dissolution kinetics under various saturation concentrations and flow conditions are characterized by the frequency parameter, Schmidt number, and Peclet number. The result severs as a basic case in determining the efficiency of drug dissolution or reconstitution that depends on various shaking methods.

  5. Molecular Recognition and Ligand Association

    NASA Astrophysics Data System (ADS)

    Baron, Riccardo; McCammon, J. Andrew

    2013-04-01

    We review recent developments in our understanding of molecular recognition and ligand association, focusing on two major viewpoints: (a) studies that highlight new physical insight into the molecular recognition process and the driving forces determining thermodynamic signatures of binding and (b) recent methodological advances in applications to protein-ligand binding. In particular, we highlight the challenges posed by compensating enthalpic and entropic terms, competing solute and solvent contributions, and the relevance of complex configurational ensembles comprising multiple protein, ligand, and solvent intermediate states. As more complete physics is taken into account, computational approaches increase their ability to complement experimental measurements, by providing a microscopic, dynamic view of ensemble-averaged experimental observables. Physics-based approaches are increasingly expanding their power in pharmacology applications.

  6. What are Nuclear Receptor Ligands?

    PubMed Central

    Sladek, Frances M.

    2010-01-01

    Nuclear receptors (NRs) are a family of highly conserved transcription factors that regulate transcription in response to small lipophilic compounds. They play a role in every aspect of development, physiology and disease in humans. They are also ubiquitous in and unique to the animal kingdom suggesting that they may have played an important role in their evolution. In contrast to the classical endocrine receptors that originally defined the family, recent studies suggest that the first NRs might have been sensors of their environment, binding ligands that were external to the host organism. The purpose of this review is to provide a broad perspective on NR ligands and address the issue of exactly what constitutes a NR ligand from historical, biological and evolutionary perspectives. This discussion will lay the foundation for subsequent reviews in this issue as well as pose new questions for future investigation. PMID:20615454

  7. Fluorescent ligands for adenosine receptors.

    PubMed

    Kozma, Eszter; Jayasekara, P Suresh; Squarcialupi, Lucia; Paoletta, Silvia; Moro, Stefano; Federico, Stephanie; Spalluto, Giampiero; Jacobson, Kenneth A

    2013-01-01

    Interest is increasing in developing fluorescent ligands for characterization of adenosine receptors (ARs), which hold a promise of usefulness in the drug discovery process. The size of a strategically labeled AR ligand can be greatly increased after the attachment of a fluorophore. The choice of dye moiety (e.g. Alexa Fluor 488), attachment point and linker length can alter the selectivity and potency of the parent molecule. Fluorescent derivatives of adenosine agonists and antagonists (e.g. XAC and other heterocyclic antagonist scaffolds) have been synthesized and characterized pharmacologically. Some are useful AR probes for flow cytometry, fluorescence correlation spectroscopy, fluorescence microscopy, fluorescence polarization, fluorescence resonance energy transfer, and scanning confocal microscopy. Thus, the approach of fluorescent labeled GPCR ligands, including those for ARs, is a growing dynamic research field.

  8. Why mercury prefers soft ligands

    SciTech Connect

    Riccardi, Demian M; Guo, Hao-Bo; Gu, Baohua; Parks, Jerry M; Summers, Anne; Miller, S; Liang, Liyuan; Smith, Jeremy C

    2013-01-01

    Mercury (Hg) is a major global pollutant arising from both natural and anthropogenic sources. Defining the factors that determine the relative affinities of different ligands for the mercuric ion, Hg2+, is critical to understanding its speciation, transformation, and bioaccumulation in the environment. Here, we use quantum chemistry to dissect the relative binding free energies for a series of inorganic anion complexes of Hg2+. Comparison of Hg2+ ligand interactions in the gaseous and aqueous phases shows that differences in interactions with a few, local water molecules led to a clear periodic trend within the chalcogenide and halide groups and resulted in the well-known experimentally observed preference of Hg2+ for soft ligands such as thiols. Our approach establishes a basis for understanding Hg speciation in the biosphere.

  9. Dissolution of Arsenic Minerals Mediated by Dissimilatory Arsenate Reducing Bacteria: Estimation of the Physiological Potential for Arsenic Mobilization

    PubMed Central

    Lukasz, Drewniak; Liwia, Rajpert; Aleksandra, Mantur; Aleksandra, Sklodowska

    2014-01-01

    The aim of this study was characterization of the isolated dissimilatory arsenate reducing bacteria in the context of their potential for arsenic removal from primary arsenic minerals through reductive dissolution. Four strains, Shewanella sp. OM1, Pseudomonas sp. OM2, Aeromonas sp. OM4, and Serratia sp. OM17, capable of anaerobic growth with As (V) reduction, were isolated from microbial mats from an ancient gold mine. All of the isolated strains: (i) produced siderophores that promote dissolution of minerals, (ii) were resistant to dissolved arsenic compounds, (iii) were able to use the dissolved arsenates as the terminal electron acceptor, and (iii) were able to use copper minerals containing arsenic minerals (e.g., enargite) as a respiratory substrate. Based on the results obtained in this study, we postulate that arsenic can be released from some As-bearing polymetallic minerals (such as copper ore concentrates or middlings) under reductive conditions by dissimilatory arsenate reducers in indirect processes. PMID:24724102

  10. Dissolution of arsenic minerals mediated by dissimilatory arsenate reducing bacteria: estimation of the physiological potential for arsenic mobilization.

    PubMed

    Lukasz, Drewniak; Liwia, Rajpert; Aleksandra, Mantur; Aleksandra, Sklodowska

    2014-01-01

    The aim of this study was characterization of the isolated dissimilatory arsenate reducing bacteria in the context of their potential for arsenic removal from primary arsenic minerals through reductive dissolution. Four strains, Shewanella sp. OM1, Pseudomonas sp. OM2, Aeromonas sp. OM4, and Serratia sp. OM17, capable of anaerobic growth with As (V) reduction, were isolated from microbial mats from an ancient gold mine. All of the isolated strains: (i) produced siderophores that promote dissolution of minerals, (ii) were resistant to dissolved arsenic compounds, (iii) were able to use the dissolved arsenates as the terminal electron acceptor, and (iii) were able to use copper minerals containing arsenic minerals (e.g., enargite) as a respiratory substrate. Based on the results obtained in this study, we postulate that arsenic can be released from some As-bearing polymetallic minerals (such as copper ore concentrates or middlings) under reductive conditions by dissimilatory arsenate reducers in indirect processes.

  11. A novel off-center paddle impeller (OPI) dissolution testing system for reproducible dissolution testing of solid dosage forms.

    PubMed

    Wang, Yimin; Armenante, Piero M

    2012-02-01

    Dissolution testing is routinely conducted in the pharmaceutical industry to provide in vitro drug release information for quality control purposes. The most common dissolution testing system for solid dosage forms is the United States Pharmacopeia (USP) Dissolution Testing Apparatus 2. This apparatus is very sensitive to the initial location of the tablet, which cannot be controlled because the tablet is dropped into the vessel at the beginning of the test and it may rest at random locations at the vessel's bottom. In this work, a modified Apparatus 2 in which the impeller was placed 8 mm off center in the vessel was designed and tested. This new design was termed "OPI" for "off-center paddle impeller." Dissolution tests were conducted with the OPI apparatus for nine different tablet locations using both disintegrating tablets (prednisone) and nondisintegrating tablets (salicylic acid). The dissolution profiles in the OPI apparatus were largely independent of the tablet location at the vessel's bottom, whereas those obtained in the Standard System generated statistically different profiles depending on the tablet location. The newly proposed OPI system can effectively eliminate artifacts generated by random settling of the tablet at the vessel's bottom, thus making the test more robust.

  12. The relationship between dissolution, gas oversaturation and outgassing of solutions determined by Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS).

    PubMed

    Fitzpatrick, Dara; Evans-Hurson, Rachel; Krüse, Jacob; Vos, Bastiaan; McSweeney, Seán; Casaubieilh, Pierre; O'Gorman, Eadaoin

    2013-09-01

    The addition of a solute to a solvent is known to reduce the solubility of dissolved gases in solution which leads to gas oversaturation and outgassing of the solvent. The importance of the processes involved have received relatively little attention due to a limited capacity to elucidate their effects in real time. Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS) is a recently introduced acoustic approach which can monitor changes in the compressibility of a solvent due to outgassing. BARDS spectra show that a time dependent and quantitative reduction in gas oversaturation, following the dissolution of a simple salt, takes place over several hours. It is shown how vigorous agitation quickly equilibrates a solution, post dissolution, by removing gas oversaturation consistently. The level of oversaturation can be elucidated by further dissolving a marker compound into a solution consecutively. BARDS spectra indicate that the dissolution of a compound produces a consistent and quantifiable oversaturation of a solvent and a consistent and quantifiable outgassing. Low frequency sonication in an immersion bath is also shown to play no significant role in removing gas oversaturation post dissolution.

  13. Role of microbial iron reduction in the dissolution of iron hydroxysulfate minerals

    USGS Publications Warehouse

    Jones, E.J.P.; Nadeau, T.-L.; Voytek, M.A.; Landa, E.R.

    2006-01-01

    Iron-hydroxysulfate minerals can be important hosts for metals such as lead, mercury, copper, zinc, silver, chromium, arsenic, and selenium and for radionuclides such as 226Ra. These mineral-bound contaminants are considered immobilized under oxic conditions. However, when anoxic conditions develop, the activities of sulfate- or iron-reducing bacteria could result in mineral dissolution, releasing these bound contaminants. Reduction of structural sulfate in the iron-hydroxysulfate mineral jarosite by sulfate-reducing bacteria has previously been demonstrated. The primary objective of this work was to evaluate the potential for anaerobic dissolution of the iron-hydroxysulfate minerals jarosite and schwertmannite at neutral PH by iron-reducing bacteria. Mineral dissolution was tested using a long-term cultivar, Geobacter metallireducens strain GS-15, and a fresh isolate Geobacter sp. strain ENN1, previously undescribed. ENN1 was isolated from the discharge site of Shadle Mine, in the southern anthracite coalfield of Pennsylvania, where schwertmannite was the predominant iron-hydroxysulfate mineral. When jarosite from Elizabeth Mine (Vermont) was provided as the sole terminal electron acceptor, resting cells of both G. metallireducens and ENN1 were able to reduce structural Fe(III), releasing Fe+2, SO4-2, and K+ ions. A lithified jarosite sample from Utah was more resistant to microbial attack, but slow release of Fe+2 was observed. Neither bacterium released Fe+2 from poorly crystalline synthetic schwertmannite. Our results indicate that exposure of jarosite to iron-reducing conditions at neutral pH is likely to promote the mobility of hazardous constituents and should therefore be considered in evaluating waste disposal and/or reclamation options involving jarosite-bearing materials.

  14. Role of microbial iron reduction in the dissolution of iron hydroxysulfate minerals

    NASA Astrophysics Data System (ADS)

    Jones, Elizabeth J. P.; Nadeau, Tracie-Lynn; Voytek, Mary A.; Landa, Edward R.

    2006-03-01

    Iron-hydroxysulfate minerals can be important hosts for metals such as lead, mercury, copper, zinc, silver, chromium, arsenic, and selenium and for radionuclides such as 226Ra. These mineral-bound contaminants are considered immobilized under oxic conditions. However, when anoxic conditions develop, the activities of sulfate- or iron-reducing bacteria could result in mineral dissolution, releasing these bound contaminants. Reduction of structural sulfate in the iron-hydroxysulfate mineral jarosite by sulfate-reducing bacteria has previously been demonstrated. The primary objective of this work was to evaluate the potential for anaerobic dissolution of the iron-hydroxysulfate minerals jarosite and schwertmannite at neutral pH by iron-reducing bacteria. Mineral dissolution was tested using a long-term cultivar, Geobacter metallireducens strain GS-15, and a fresh isolate Geobacter sp. strain ENN1, previously undescribed. ENN1 was isolated from the discharge site of Shadle Mine, in the southern anthracite coalfield of Pennsylvania, where schwertmannite was the predominant iron-hydroxysulfate mineral. When jarosite from Elizabeth Mine (Vermont) was provided as the sole terminal electron acceptor, resting cells of both G. metallireducens and ENN1 were able to reduce structural Fe(III), releasing Fe+2, SO4-2, and K+ ions. A lithified jarosite sample from Utah was more resistant to microbial attack, but slow release of Fe+2 was observed. Neither bacterium released Fe+2 from poorly crystalline synthetic schwertmannite. Our results indicate that exposure of jarosite to iron-reducing conditions at neutral pH is likely to promote the mobility of hazardous constituents and should therefore be considered in evaluating waste disposal and/or reclamation options involving jarosite-bearing materials.

  15. A model for reaction-assisted polymer dissolution in LIGA.

    SciTech Connect

    Larson, Richard S.

    2004-05-01

    A new chemically-oriented mathematical model for the development step of the LIGA process is presented. The key assumption is that the developer can react with the polymeric resist material in order to increase the solubility of the latter, thereby partially overcoming the need to reduce the polymer size. The ease with which this reaction takes place is assumed to be determined by the number of side chain scissions that occur during the x-ray exposure phase of the process. The dynamics of the dissolution process are simulated by solving the reaction-diffusion equations for this three-component, two-phase system, the three species being the unreacted and reacted polymers and the solvent. The mass fluxes are described by the multicomponent diffusion (Stefan-Maxwell) equations, and the chemical potentials are assumed to be given by the Flory-Huggins theory. Sample calculations are used to determine the dependence of the dissolution rate on key system parameters such as the reaction rate constant, polymer size, solid-phase diffusivity, and Flory-Huggins interaction parameters. A simple photochemistry model is used to relate the reaction rate constant and the polymer size to the absorbed x-ray dose. The resulting formula for the dissolution rate as a function of dose and temperature is ?t to an extensive experimental data base in order to evaluate a set of unknown global parameters. The results suggest that reaction-assisted dissolution is very important at low doses and low temperatures, the solubility of the unreacted polymer being too small for it to be dissolved at an appreciable rate. However, at high doses or at higher temperatures, the solubility is such that the reaction is no longer needed, and dissolution can take place via the conventional route. These results provide an explanation for the observed dependences of both the dissolution rate and its activation energy on the absorbed dose.

  16. Enhancement of Loperamide Dissolution Rate by Liquisolid Compact Technique

    PubMed Central

    Venkateswarlu, Kambham; Preethi, Jami Komala; Chandrasekhar, Kothapalli Bonnoth

    2016-01-01

    Purpose: The aim of present study was to improve the dissolution rate of poorly soluble drug Loperamide (LPM) by liquisolid compact technique. Methods: Liquisolid compacts of LPM were prepared using Propylene glycol (PG) as a solvent, Avicel pH 102 as carrier, Aerosil as coating material and Sodium Starch Glycolate (SSG) as superdisintegrant. Interactions between the drug and excipients were examined by Fourier Transform Infrared (FTIR) spectroscopy. The dissolution studies for LPM liquisolid formulation, marketed product and pure drug were carried out in pH 1.2 HCl buffer as dissolution media. Results: Results confirmed the absence of chemical interactions between the drug and excipients. From the solubility studies, it was observed the LPM was highly soluble in PG thereby it was selected as a solvent. The dissolution efficiency of LPM at 15 min was increased from 9.99 % for pure drug and 54.57% for marketed product to 86.81% for the tablets prepared by liquisolid compact technique. Stability studies showed no significant change in percent cumulative drug release, hardness, disintegration time, friability and drug content for 3 months. Conclusion: Formulation F2 showed significant increase in dissolution rate compared to the marketed product at pH 1.2 where LPM is largely absorbed. Around 90% of the drug was released from F2 in 30 min compared to the marketed product and it might be due to the increased wetting and surface area of the particles. Hence, the liquisolid compact technique appears to be a promising approach for improving the dissolution rate of poorly soluble drug. PMID:27766222

  17. Principles of Calcite Dissolution in Human and Artificial Otoconia

    PubMed Central

    Walther, Leif Erik; Blödow, Alexander; Buder, Jana; Kniep, Rüdiger

    2014-01-01

    Human otoconia provide mechanical stimuli to deflect hair cells of the vestibular sensory epithelium for purposes of detecting linear acceleration and head tilts. During lifetime, the volume and number of otoconia are gradually reduced. In a process of degeneration morphological changes occur. Structural changes in human otoconia are assumed to cause vertigo and balance disorders such as benign paroxysmal positional vertigo (BPPV). The aim of this study was to investigate the main principles of morphological changes in human otoconia in dissolution experiments by exposure to hydrochloric acid, EDTA, demineralized water and completely purified water respectively. For comparison reasons artificial (biomimetic) otoconia (calcite gelatin nanocomposits) and natural calcite were used. Morphological changes were detected in time steps by the use of environmental scanning electron microscopy (ESEM). Under in vitro conditions three main dissolution mechanisms were identified as causing characteristic morphological changes of the specimen under consideration: pH drops in the acidic range, complex formation with calcium ions and changes of ion concentrations in the vicinity of otoconia. Shifts in pH cause a more uniform reduction of otoconia size (isotropic dissolution) whereas complexation reactions and changes of the ionic concentrations within the surrounding medium bring about preferred attacks at specific areas (anisotropic dissolution) of human and artificial otoconia. Owing to successive reduction of material, all the dissolution mechanisms finally produce fragments and remnants of otoconia. It can be assumed that the organic component of otoconia is not significantly attacked under the given conditions. Artificial otoconia serve as a suitable model system mimicking chemical attacks on biogenic specimens. The underlying principles of calcite dissolution under in vitro conditions may play a role in otoconia degeneration processes such as BPPV. PMID:25048115

  18. The many facets of Notch ligands

    PubMed Central

    D'souza, Brendan; Miyamoto, Alison; Weinmaster, Gerry

    2009-01-01

    The Notch signaling pathway regulates a diverse array of cell types and cellular processes and is tightly regulated by ligand binding. Both canonical and noncanonical Notch ligands have been identified that may account for some of the pleiotropic nature associated with Notch signaling. This review focuses on the molecular mechanisms by which Notch ligands function as signaling agonists and antagonists, and discusses different modes of activating ligands as well as findings that support intrinsic ligand signaling activity independent of Notch. Post-translational modification, proteolytic processing, endocytosis and membrane trafficking, as well as interactions with the actin cytoskeleton may contribute to the recently appreciated multi-functionality of Notch ligands. The regulation of Notch ligand expression by other signaling pathways provides a mechanism to coordinate Notch signaling with multiple cellular and developmental cues. The association of Notch ligands with inherited human disorders and cancer highlights the importance of understanding the molecular nature and activities intrinsic to Notch ligands. PMID:18758484

  19. Multifunctional Ligands in Transition Metal Catalysis

    SciTech Connect

    Crabtree, Robert H

    2011-01-01

    Sophisticated ligands are now being designed that do far more than just fulfil their traditional spectator roles by binding to the metal and providing a sterically-defined binding pocket for the substrate in homogeneous transition metal catalysis. This Focus review emphasizes selected cases in which ligands carry additional functional groups that change the properties of the ligand as a result of an external stimulus or undergo catalytically-relevant ligand-based reactivity. These include proton responsive ligands capable of gaining or losing one or more protons, ligands having a hydrogen bonding function, electroresponsive ligands capable of gaining or losing one or more electrons, and photoresponsive ligands capable of undergoing a useful change of properties upon irradiation. Molecular recognition ligands and proton coupled electron transfer (PCET) are briefly discussed.

  20. A porous silica rock ("tripoli") in the footwall of the Jurassic Úrkút manganese deposit, Hungary: composition, and origin through carbonate dissolution

    USGS Publications Warehouse

    Polgari, Marta; Szabo, Zoltan; Szabo-Drubina, Magda; Hein, James R.; Yeh, Hsueh-Wen

    2005-01-01

    The mineralogical, chemical, and isotopic compositions were determined for a white tripoli from the footwall of the Jurassic Úrkút Mn-oxide ore deposit in the Bakony Mountains, Hungary. The tripoli consists of quartz and chalcedony, with SiO2 contents up to 100 wt.%; consequently, trace-element contents are very low. Oxygen isotopes and quartz crystallinity indicate a low-temperature diagenetic origin for this deposit. The tripoli was formed by dissolution of the carbonate portion of the siliceous (sponge spicules) Isztimér Limestone. Dissolution of the carbonate was promoted by inorganic and organic acids generated during diagensis and left a framework composed of diagenetic silica that preserved the original volume of the limestone layer. The relative enrichment of silica and high porosity is the result of that carbonate dissolution. The silty texture of this highly friable rock is due to the structurally weak silica framework.

  1. Ligand-induced Epitope Masking

    PubMed Central

    Mould, A. Paul; Askari, Janet A.; Byron, Adam; Takada, Yoshikazu; Jowitt, Thomas A.; Humphries, Martin J.

    2016-01-01

    We previously demonstrated that Arg-Gly-Asp (RGD)-containing ligand-mimetic inhibitors of integrins are unable to dissociate pre-formed integrin-fibronectin complexes (IFCs). These observations suggested that amino acid residues involved in integrin-fibronectin binding become obscured in the ligand-occupied state. Because the epitopes of some function-blocking anti-integrin monoclonal antibodies (mAbs) lie near the ligand-binding pocket, it follows that the epitopes of these mAbs may become shielded in the ligand-occupied state. Here, we tested whether function-blocking mAbs directed against α5β1 can interact with the integrin after it forms a complex with an RGD-containing fragment of fibronectin. We showed that the anti-α5 subunit mAbs JBS5, SNAKA52, 16, and P1D6 failed to disrupt IFCs and hence appeared unable to bind to the ligand-occupied state. In contrast, the allosteric anti-β1 subunit mAbs 13, 4B4, and AIIB2 could dissociate IFCs and therefore were able to interact with the ligand-bound state. However, another class of function-blocking anti-β1 mAbs, exemplified by Lia1/2, could not disrupt IFCs. This second class of mAbs was also distinguished from 13, 4B4, and AIIB2 by their ability to induce homotypic cell aggregation. Although the epitope of Lia1/2 was closely overlapping with those of 13, 4B4, and AIIB2, it appeared to lie closer to the ligand-binding pocket. A new model of the α5β1-fibronectin complex supports our hypothesis that the epitopes of mAbs that fail to bind to the ligand-occupied state lie within, or very close to, the integrin-fibronectin interface. Importantly, our findings imply that the efficacy of some therapeutic anti-integrin mAbs could be limited by epitope masking. PMID:27484800

  2. Spent fuel dissolution studies FY 1991 to 1994

    SciTech Connect

    Gray, W.J.; Wilson, C.N.

    1995-12-01

    Dissolution and transport as a result of groundwater flow are generally accepted as the primary mechanisms by which radionuclides from spent fuel placed in a geologic repository could be released to the biosphere. To help provide a source term for performance assessment calculations, dissolution studies on spent fuel and unirradiated uranium oxides have been conducted over the past few years at Pacific Northwest National Laboratory (PNNL) in support of the Yucca Mountain Site Characterization Project. This report describes work for fiscal years 1991 through 1994. The objectives of these studies and the associated conclusions, which were based on the limited number of tests conducted so far, are described in the following subsections.

  3. Illite Dissolution Rates and Equation (100 to 280 dec C)

    DOE Data Explorer

    Carroll, Susan

    2014-10-17

    The objective of this suite of experiments was to develop a useful kinetic dissolution expression for illite applicable over an expanded range of solution pH and temperature conditions representative of subsurface conditions in natural and/or engineered geothermal reservoirs. Using our new data, the resulting rate equation is dependent on both pH and temperature and utilizes two specific dissolution mechanisms (a “neutral” and a “basic” mechanism). The form of this rate equation should be easily incorporated into most existing reactive transport codes for to predict rock-water interactions in EGS shear zones.

  4. Effects of alteration product precipitation on glass dissolution

    SciTech Connect

    Strachan, Denis M.; Neeway, James J.

    2014-06-01

    Understanding the mechanisms that control the durability of nuclear waste glass is paramount if reliable models are to be constructed so that the glass dissolution rate in a given geological repository can be calculated. Presently, it is agreed that (boro)silicate glasses dissolve in water at a rate dependent on the solution concentration of orthosilicic acid (H4SiO4) with higher [H4SiO4] leading to lower dissolution rates. Once the reaction has slowed as a result of the buildup of H4SiO4, another increase in the rate has been observed that corresponds to the precipitation of certain silica-bearing alteration products. However, it has also been observed that the concentration of silica-bearing solution species does not significantly decrease, indicating saturation, while other glass tracer elements concentrations continue to increase, indicating that the glass is still dissolving. In this study, we have used the Geochemist’s Workbench code to investigate the relationship between glass dissolution rates and the precipitation rate of a representative zeolitic silica-bearing alteration product, analcime [Na(AlSi2O6)∙H2O]. To simplify the calculations, we suppressed all alteration products except analcime, gibbsite (Al(OH)3), and amorphous silica. The pseudo-equilibrium-constant matrix for amorphous silica was substituted for the glass pseudo-equilibrium-constant matrix because it has been shown that silicate glasses act as a silica-only solid with respect to kinetic considerations. In this article, we present the results of our calculations of the glass dissolution rate at different values for the analcime precipitation rate constant and the effects of varying the glass dissolution rate constant at a constant analcime precipitation rate constant. From the simulations we conclude, firstly, that the rate of glass dissolution is dependent on the kinetics of

  5. Biodegradation and dissolution of polyaromatic hydrocarbons by Stenotrophomonas sp.

    PubMed

    Tiwari, Bhagyashree; Manickam, N; Kumari, Smita; Tiwari, Akhilesh

    2016-09-01

    The aim of this work was to study the biodegradation capabilities of a locally isolated bacterium, Stenotrophomonas sp. strain IITR87 to degrade the polycyclic aromatic hydrocarbons and also check the preferential biodegradation of polycyclic aromatic hydrocarbons (PAHs). From preferential substrate degradation studies, it was found that Stenotrophomonas sp. strain IITR87 first utilized phenanthrene (three membered ring), followed by pyrene (four membered ring), then benzo[α]pyrene (five membered ring). Dissolution study of PAHs with surfactants, rhamnolipid and tritonX-100 showed that the dissolution of PAHs increased in the presence of surfactants. PMID:27342606

  6. Rosetta Ligand docking with flexible XML protocols.

    PubMed

    Lemmon, Gordon; Meiler, Jens

    2012-01-01

    RosettaLigand is premiere software for predicting how a protein and a small molecule interact. Benchmark studies demonstrate that 70% of the top scoring RosettaLigand predicted interfaces are within 2Å RMSD from the crystal structure [1]. The latest release of Rosetta ligand software includes many new features, such as (1) docking of multiple ligands simultaneously, (2) representing ligands as fragments for greater flexibility, (3) redesign of the interface during docking, and (4) an XML script based interface that gives the user full control of the ligand docking protocol. PMID:22183535

  7. Multicoordinate ligands for actinide/lanthanide separations.

    PubMed

    Dam, Henk H; Reinhoudt, David N; Verboom, Willem

    2007-02-01

    In nuclear waste treatment processes there is a need for improved ligands for the separation of actinides (An(III)) and lanthanides (Ln(III)). Several research groups are involved in the design and synthesis of new An(III) ligands and in the confinement of these and existing An(III) ligands onto molecular platforms giving multicoordinate ligands. The preorganization of ligands considerably improves the An(III) extraction properties, which are largely dependent on the solubility and rigidity of the platform. This tutorial review summarizes the most important An(III) ligands with emphasis on the preorganization strategy using (macrocyclic) platforms.

  8. Revisiting classical silicate dissolution rate laws under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Pollet-Villard, Marion; Daval, Damien; Saldi, Giuseppe; Knauss, Kevin; Wild, Bastien; Fritz, Bertrand

    2015-04-01

    In the context of geothermal energy, the relative intensities of primary mineral leaching and secondary mineral precipitation can affect porosity and permeability of the reservoir, thereby influencing its hydraulic performance and the efficiency of the geothermal power station. That is why the prediction of reaction kinetics of fluid/rock interactions represents a critical issue in this context. Moreover, in several geothermal systems such as the one of Soultz-sous-Forêts (Alsace, France), the circulation of aqueous fluids induces only modest modifications of their chemical composition. Therefore, fluid-rock interactions take place at close-to-equilibrium conditions, where the rate-affinity relations are poorly known and intensively debated [1]. To describe more precisely the dissolution processes, our strategy consists in investigating the dissolution of the main cleavages of K-spar minerals (one of the prevalent primary minerals in the reservoir of Soultz-sous-Forêts geothermal system) over a wide range of Gibbs free energy (ΔG) conditions. The aims are to decipher the impact of crystallographic orientation and microstructural surface modifications on the dissolution kinetics and to propose a relation between K-spar dissolution rate and ΔG. Our experimental work relies on a coupled approach which combines classical experiments of K-spar dissolution monitored by aqueous chemical analyses (ICP-AES) and innovative techniques of nm- to μm-scale characterization of solid surface (SEM, AFM, VSI) [2]. Our results confirm that K-spar dissolution is an anisotropic process: we measure a tenfold factor between the slowest and the fastest-dissolving surfaces. Moreover, the formation of etch pits on surfaces during their alteration has been evidenced on all of the different faces that have been studied. This complex evolution of the surface topography casts doubt of the relevance of a surface model based on shrinking particles and represents a possible cause of an

  9. Role of microbial iron reduction in the dissolution of iron hydroxysulfate minerals - article no. G01012

    SciTech Connect

    Jones, E.J.P.; Nadeau, T.L.; Voytek, M.A.; Landa, E.R.

    2006-03-28

    Reduction of structural sulfate in the iron-hydroxysulfate mineral jarosite by sulfate-reducing bacteria has previously been demonstrated. The primary objective of this work was to evaluate the potential for anaerobic dissolution of the iron-hydroxysulfate minerals jarosite and schwertmannite at neutral pH by iron-reducing bacteria. Mineral dissolution was tested using a long-term cultivar, Geobacter metallireducens strain GS-15, and a fresh isolate Geobacter sp. strain ENN1, previously undescribed. ENN1 was isolated from the discharge site of Shadle Mine, in the southern anthracite coalfield of Pennsylvania, where schwertmannite was the predominant iron-hydroxysulfate mineral. When jarosite from Elizabeth Mine (Vermont) was provided as the sole terminal electron acceptor, resting cells of both G. metallireducens and ENN1 were able to reduce structural Fe(III), releasing Fe{sup +2}, SO{sub 4}{sup -2}, and K{sup +} ions. A lithified jarosite sample from Utah was more resistant to microbial attack, but slow release of Fe{sup +2} was observed. Neither bacterium released Fe{sup +2} from poorly crystalline synthetic schwertmannite. Our results indicate that exposure of jarosite to iron-reducing conditions at neutral pH is likely to promote the mobility of hazardous constituents and should therefore be considered in evaluating waste disposal and/or reclamation options involving jarosite-bearing materials.

  10. [Effects of temperature and PH on dissolution kinetics of methotrexate in aqueous media].

    PubMed

    Houngbossa, K; Guenzet, J; Bourin, M

    1996-01-01

    In vitro dissolution kinetics of Methotrexate have been analysed at different temperatures in water at pH 1.5. After giving rise to the dissolution reaction, it has been possible to follow up the kinetic of dissolution and calculate energy activation. The pH variation allows us also to appreciate the constant behaviour of dissolution at temperature 310 K (37 degrees). Weilbull equation is valid with success for dissolution reaction as well during temperature variation and different values of pH. In both cases the Weibull constant b has been calculated and compared to constant dissolution K.

  11. Polypharmacology of dopamine receptor ligands.

    PubMed

    Butini, S; Nikolic, K; Kassel, S; Brückmann, H; Filipic, S; Agbaba, D; Gemma, S; Brogi, S; Brindisi, M; Campiani, G; Stark, H

    2016-07-01

    Most neurological diseases have a multifactorial nature and the number of molecular mechanisms discovered as underpinning these diseases is continuously evolving. The old concept of developing selective agents for a single target does not fit with the medical need of most neurological diseases. The development of designed multiple ligands holds great promises and appears as the next step in drug development for the treatment of these multifactorial diseases. Dopamine and its five receptor subtypes are intimately involved in numerous neurological disorders. Dopamine receptor ligands display a high degree of cross interactions with many other targets including G-protein coupled receptors, transporters, enzymes and ion channels. For brain disorders like Parkinsońs disease, schizophrenia and depression the dopaminergic system, being intertwined with many other signaling systems, plays a key role in pathogenesis and therapy. The concept of designed multiple ligands and polypharmacology, which perfectly meets the therapeutic needs for these brain disorders, is herein discussed as a general ligand-based concept while focusing on dopaminergic agents and receptor subtypes in particular. PMID:27234980

  12. A race for RAGE ligands.

    PubMed

    Schleicher, Erwin D

    2010-08-01

    In experimental animals a causal involvement of the multiligand receptor for advanced glycation end products (RAGE) in the development of diabetic vascular complications has been demonstrated. However, the nature of RAGE ligands present in patients with diabetic nephropathy has not yet been defined; this leaves open the relevance of the RAGE system to the human disease.

  13. Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands.

    PubMed

    Fliedel, Christophe; Ghisolfi, Alessio; Braunstein, Pierre

    2016-08-24

    The aim of this review is to highlight how the diversity generated by N-substitution in the well-known short-bite ligand bis(diphenylphosphino)amine (DPPA) allows a fine-tuning of the ligand properties and offers a considerable scope for tailoring the properties and applications of their corresponding metal complexes. The various N-substituents include nitrogen-, oxygen-, phosphorus-, sulfur-, halogen-, and silicon-based functionalities and directly N-bound metals. Multiple DPPA-type ligands linked through an organic spacer and N-functionalized DRPA-type ligands, in which the PPh2 substituents are replaced by PR2 (R = alkyl, benzyl) groups, are also discussed. Owing to the considerable diversity of N-functionalized DPPA-type ligands available, the applications of their mono- and polynuclear metal complexes are very diverse and range from homogeneous catalysis with well-defined or in situ generated (pre)catalysts to heterogeneous catalysis and materials science. In particular, sustained interest for DPPA-type ligands has been motivated, at least in part, by their ability to promote selective ethylene tri- or tetramerization in combination with chromium. Ligands and metal complexes where the N-substituent is a pure hydrocarbon group (as opposed to N-functionalization) are outside the scope of this review. However, when possible, a comparison between the catalytic performances of N-functionalized systems with those of their N-substituted analogs will be provided. PMID:27456550

  14. Modeling NAPL dissolution from pendular rings in idealized porous media

    EPA Science Inventory

    The rate of NAPL dissolution often governs the clean-up time for subsurface hazardous waste sites. Most formulations for estimating this rate are empirical and assume that the NAPL is the non-wetting fluid. However, field evidence suggests that some waste sites might be organic...

  15. Adolescent Sexuality and the Risk of Marital Dissolution

    ERIC Educational Resources Information Center

    Paik, Anthony

    2011-01-01

    This research investigates whether first sexual intercourse during adolescence is associated with increased risk of first marriage dissolution and tests whether the results are consistent with causal or selection explanations. Drawing on a sample of 3,793 ever-married women from the 2002 National Survey of Family Growth, this study estimated…

  16. Adolescents' Explanations for Romantic Dissolutions: A Developmental Perspective

    ERIC Educational Resources Information Center

    Connolly, Jennifer; McIsaac, Caroline

    2009-01-01

    Our objective was to examine the prevalence and developmental significance of romantic break-ups in adolescence, a relatively unexplored area of study. We examined their occurrence in a sample of 910 adolescents, first noting the frequency of these events across age, gender, and romantic experience, and then analyzing the dissolution explanations…

  17. Late Pleistocene carbonate dissolution in the Venezuela Basin, Caribbean Sea

    SciTech Connect

    Cofer-Shabica, N.B.; Peterson, L.C.

    1985-01-01

    Piston cores from water depths greater than 4000 m in the Venezuela Basin (Caribbean Sea) provide continuous late Pleistocene records of carbonate dissolution and accumulation. The authors examination of multiple dissolution indices indicate that, at least for the last 150,000 years, dissolution of carbonate in the Venezuela Basin has been more intense during interglacial than glacial periods, a pattern opposite to more general observations from the deep Atlantic and Gulf of Mexico. By virtue of its shallow sill depth (1815 m), the Venezuela Basin is relatively isolated from the mainstream of Atlantic thermohaline circulation, and presently is filled with homogeneous, relatively warm (3.8/sup 0/C) waters primarily derived from Upper North Atlantic Deep Water. During the last glacial, the enhanced preservation of carbonate in the Venezuela Basin suggests the presence of a less corrosive, more oxygenated water mass in the Atlantic near sill depth. However, this simple interpretations is potentially complicated by past changes in the rain of biogenic materials from surface waters to the deep basin in what must be an essentially closed system below sill depth. Their observations of increased interglacial dissolution may help to explain previously noted discrepancies in the local glacial to interglacial amplitude of delta/sup 18/O variations recorded by coccoliths and planktonic foraminifera.

  18. Students' Spontaneous Use of a Particulate Model for Dissolution.

    ERIC Educational Resources Information Center

    Selley, Nicholas J.

    2001-01-01

    Studies students aged 12 to 14 years (n=217) representing a wide ability range. Analyzes the responses of participants to the dissolution of a solid in both cold and warm water. Findings have implications for the teaching of all science theory but especially for conveying the purpose of models and the process of modeling. (Contains 29 references.)…

  19. Dissolution kinetics of a sintered molybdenum coating applied on ceramics

    SciTech Connect

    Kuz`ko, V.S.

    1994-11-01

    Using weighing and corrosion diagrams, the etching parameters are determined for a sintered M-21 molybdenum coating applied to VK 94-1 vacuum-tight ceramics. Dissolution of M-21 in an alkaline solution of potassium hexacyanoferrate(III) can be treated as a corrosion process proceeding with kinetic control.

  20. Solar Radiation Management and Olivine Dissolution Methods in Climate Engineering

    NASA Astrophysics Data System (ADS)

    Kone, S.

    2014-12-01

    An overview of solar radiation management and olivine dissolution methods allows to discuss, comparatively, the benefits and consequences of these two geoengineering techniques. The combination of those two techniques allows to concomitantly act on the two main agents intervening in global warming: solar radiation and carbon dioxide. The earth surface temperature increases due mainly to carbon dioxide (a greenhouse gas) that keeps the solar radiation and causes the global warming. Two complementary methods to mitigate climate change are overviewed: SRM method, which uses injected aerosols, aims to reduce the amount of the inbound solar radiation in atmosphere; and olivine dissolution in water, a key chemical reaction envisaged in climate engineering , aiming to reduce the amount of the carbon dioxide in extracting it from atmosphere. The SRM method works on scenarios of solar radiation decrease and the olivine dissolution method works as a carbon dioxide sequestration method. Olivine dissolution in water impacts negatively on the pH of rivers but positively in counteracting ocean acidification and in transporting the silica in ocean, which has benefits for diatom shell formation.

  1. Liquisolid Tablets for Dissolution Enhancement of a Hypolipidemic Drug

    PubMed Central

    Patel, D. S.; Pipaliya, R. M.; Surti, Naazneen

    2015-01-01

    This investigation was aimed to improve the dissolution rate of the poorly soluble drug lovastatin, by formulating it as a liquisolid compact. Different liquisolid compacts were prepared using mathematical formulae to calculate the required quantities of powder and liquid ingredients to produce acceptably flowable and compressible admixture. Avicel PH 200, Cab-O-Sil, sodium starch glycolate and PEG 400 were employed as carrier, coating material, disintegrant and non-volatile liquid vehicle, respectively. The various drug to liquid and carrier to coating ratio were used to prepare liquisolid compacts. The formulated liquisolid tablets were evaluated for weight variation, hardness, drug content, friability and disintegration time. The in vitro release characteristics of the drug from tablets formulated by direct compression and liquisolid technique were compared in two different dissolution media. The tableting properties of the liquisolid compacts were within the acceptable limits and drug release rates were distinctly higher as compared to directly compressed tablets. The FTIR spectra showed no interaction between drug-excipient and disappearance of the characteristic absorption band of lovastatin in liquisolid formulations could be attributed to the formation of hydrogen bonding between the drug and liquid vehicle, which resulted in dissolution enhancement. Thus, the liquisolid technique was found to be a promising approach for improving the dissolution of a poorly soluble drug like lovastatin. PMID:26180274

  2. Subsidence hazards due to evaporite dissolution in the United States

    USGS Publications Warehouse

    Johnson, Kenneth S.

    2005-01-01

    Evaporites, including gypsum (or anhydrite) and salt, are the most soluble of common rocks; they are dissolved readily to form the same type of karst features that typically are found in limestones and dolomites, and their dissolution can locally result in major subsidence structures. The four basic requirements for evaporite dissolution to occur are: (1) a deposit of gypsum or salt; (2) water, unsaturated with CaSO4 or NaCl; (3) an outlet for escape of dissolving water; and (4) energy to cause water to flow through the system. Evaporites are present in 32 of the 48 contiguous states of the United States, and they underlie about 35–40% of the land area. Karst is known at least locally (and sometimes quite extensively) in almost all areas underlain by evaporites, and some of these karst features involve significant subsidence. The most widespread and pronounced examples of both gypsum and salt karst and subsidence are in the Permian basin of the southwestern United States, but many other areas also are significant. Human activities have caused some evaporite–subsidence development, primarily in salt deposits. Boreholes may enable (either intentionally or inadvertently) unsaturated water to flow through or against salt deposits, thus allowing development of small to large dissolution cavities. If the dissolution cavity is large enough and shallow enough, successive roof failures above the cavity can cause land subsidence or catastrophic collapse.

  3. A Dynamic Flux Dissolution Model for Oxygen Steelmaking

    NASA Astrophysics Data System (ADS)

    Kadrolkar, Ameya; Andersson, Nils Å. I.; Dogan, Neslihan

    2016-08-01

    A modified model for prediction of flux dissolution in oxygen steelmaking process is presented in this study. The aim of this paper is to introduce a procedure for simulating the amount of dissolved lime with respect to the saturation concentration of CaO by coupling the existing thermodynamic and kinetic models simultaneously. The procedure is developed to calculate the saturation concentrations/solubility of CaO in slag using thermodynamic models namely FactSage™, Cell Model, and Thermo-Calc™. Total amount of dissolved lime is evaluated by integrating solubility values in the rate equation of lime dissolution over time taking into account the effects of physical properties and temperature of slag and particle size of flux additions and validated against industrial data available in literature. Comparison between measured and calculated undissolved lime shows a good agreement between them using any thermodynamic models even though there are some differences in the predictions of saturation concentration of CaO in slag. It has been shown that two distinct control mechanisms for lime dissolution in BOF slags exist and consideration of the free lime-controlled mechanism is essential for accurate prediction of dissolution rate of lime in slag.

  4. FY 2000 Saltcake Dissolution and Feed Stability Workshop

    SciTech Connect

    Hunt, R.D.; McGinnis, C.P.; Weber, C.F.; Welch, T.D.; Jewett, J.R.

    2000-07-31

    The Tanks Focus Area (TFA) continues to work closely with the Office of River Protection (ORP) to better understand the chemistry involved with the retrieval, transport, and pretreatment of nuclear wastes at Hanford. Since a private contractor is currently responsible for the pretreatment and immobilization activities in this remediation effort, the TFA has concentrated on saltcake dissolution and waste transport at the request of the ORP. Researchers at Hanford have performed a series of dissolution experiments on actual saltcake samples. Staff members at Mississippi State University (MSU) continue to model the dissolution results with the Environmental Simulation Program (ESP), which is used extensively by ORP personnel. Several ways to improve the predictive capabilities of the ESP were identified. Since several transfer lines at Hanford have become plugged, TFA tasks at AEA Technologies, Florida International University (FIU), MSU, and Oak Ridge National Laboratory (ORNL) are investigating the behavior of the supernatants and slurries during transport. A combination of experimental and theoretical techniques is used to study the transport chemistry. This effort is expected to develop process control tools for waste transfer. The results from these TFA tasks were presented to ORP personnel during the FY 2000 Saltcake Dissolution and Feed Stability Workshop, which was held on May 16-17 in Richland, Washington. The minutes from this workshop are provided in this report.

  5. Impact of fillers on dissolution kinetic of fenofibrate dry foams.

    PubMed

    Lenz, Elisabeth; Sprunk, Angela; Kleinebudde, Peter; Page, Susanne

    2015-01-01

    Dry foam technology reveals the opportunity to improve the dissolution behavior of poorly soluble drugs tending to agglomeration due to micronization. In this study, the impact of fillers on the manufacturability, the properties of dry foams and granules as well as the dissolution kinetics of dry foam tablets was investigated using fenofibrate as a model compound. Different maltodextrins and dried glucose syrups, a maltodextrin-phosphatidylcholine complex, isomalt and a 1:1 mixture of mannitol/glucose syrup were used as filler. Within the group of maltodextrins and glucose syrups, the influences of dextrose equivalent (DE), particle morphology and botanical source of starch were investigated. Comparable macroscopic foam structures were obtained with maltodextrins and glucose syrups whereas different foam morphologies were obtained for the other fillers tested. Regarding the maltodextrins and glucose syrups, different physicochemical and particle properties had a minor impact on granule characteristics and tablet dissolution. Using the maltodextrin-phosphatidylcholine complex resulted in a low specific surface area of the granules and a slow tablet dissolution caused by a slow disintegration. In contrast, a high specific surface area and a fast release were obtained with isomalt and glucose syrup/mannitol mixture indicating that high soluble low molecular weight fillers enable the development of fast dissolving dry foam tablets. PMID:24901031

  6. Percolation model for selective dissolution of multi-component glasses

    SciTech Connect

    Kale, R.P.; Brinker, C.J.

    1995-03-01

    A percolation model is developed which accounts for most known features of the process of porous glass membrane preparation by selective dissolution of multi-component glasses. The model is founded within tile framework of the classical percolation theory, wherein the components of a glass are represented by random sites on a suitable lattice. Computer simulation is used to mirror the generation of a porous structure during the dissolution process, reproducing many of the features associated with the phenomenon. Simulation results evaluate the effect of the initial composition of the glass on the kinetics of the leaching process as well as the morphology of the generated porous structure. The percolation model establishes the porous structure as a percolating cluster of unreachable constituents in the glass. The simulation algorithm incorporates removal of both, the accessible leachable components in the glass as well as the independent clusters of unreachable components not attached to the percolating cluster. The dissolution process thus becomes limited by the conventional site percolation thresholds of the unreachable components (which restricts the formation of the porous network), as well as the leachable components (which restricts the accessibility of the solvating medium into the glass). The simulation results delineate the range of compositional variations for successful porous glass preparation and predict the variation of porosity, surface area, dissolution rates and effluent composition with initial composition and time. Results compared well with experimental studies and improved upon similar models attempted in die past.

  7. 32 CFR 202.10 - RAB adjournment and dissolution.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... supporting documentation via the chain-of-command to the Military Component's Environmental Deputy Assistant... dissolution, he or she will request, through the chain-of-command to the Military Component's Deputy Assistant... supporting documentation should be sent via the chain-of-command to the Military Component's...

  8. The dissolution of metallic zinc in D2EHPA

    SciTech Connect

    Chia, L.M.; Neira, M.P.; O`Keefe, T.J.

    1995-07-01

    The direct dissolution of zinc in an organic solution of di-(2-ethylhexyl) phosphoric acid (D2EHPA) and kerosene was studied. The objective was to gain a better understanding of the fundamentals involved in the anodic step of the galvanic stripping process. Results showed that metallic zinc does dissolve spontaneously at ambient temperature by an electrochemical mechanism and the presence of additional oxygen activated the process. When oxygen was removed by prior nitrogen sparging, dissolution did not occur indicating a depolarizing cathodic reaction is necessary. The concentration of water in the organic also affected the rate of dissolution. A factorially designed experiment was made using four variables at two levels selected by evaluating results from previous screening tests. D2EHPA concentration, surface area and agitation were all found to be significant for the values chosen. Temperature was less significant and it was found that zinc dissolution is probably a diffusion or mixed controlled process, as indicated by the calculated activation energy of 6 kcal/mole.

  9. Impact of fillers on dissolution kinetic of fenofibrate dry foams.

    PubMed

    Lenz, Elisabeth; Sprunk, Angela; Kleinebudde, Peter; Page, Susanne

    2015-01-01

    Dry foam technology reveals the opportunity to improve the dissolution behavior of poorly soluble drugs tending to agglomeration due to micronization. In this study, the impact of fillers on the manufacturability, the properties of dry foams and granules as well as the dissolution kinetics of dry foam tablets was investigated using fenofibrate as a model compound. Different maltodextrins and dried glucose syrups, a maltodextrin-phosphatidylcholine complex, isomalt and a 1:1 mixture of mannitol/glucose syrup were used as filler. Within the group of maltodextrins and glucose syrups, the influences of dextrose equivalent (DE), particle morphology and botanical source of starch were investigated. Comparable macroscopic foam structures were obtained with maltodextrins and glucose syrups whereas different foam morphologies were obtained for the other fillers tested. Regarding the maltodextrins and glucose syrups, different physicochemical and particle properties had a minor impact on granule characteristics and tablet dissolution. Using the maltodextrin-phosphatidylcholine complex resulted in a low specific surface area of the granules and a slow tablet dissolution caused by a slow disintegration. In contrast, a high specific surface area and a fast release were obtained with isomalt and glucose syrup/mannitol mixture indicating that high soluble low molecular weight fillers enable the development of fast dissolving dry foam tablets.

  10. Modification of fracture surfaces by dissolution. Part II

    SciTech Connect

    Johnson, B.

    1983-01-01

    This study focuses upon how and to what extent dissolution related fluid/rock interactions modify the morphology and roughness of surfaces on Sioux Quartzite. Dissolution experiments consisted of reacting small discs of Sioux Quartzite in sealed gold capsules containing either distilled water or 0.05 N to 4.0 N aqueous solutions of Na/sub 2/CO/sub 3/. Samples were reacted at 200/sup 0/C and 20 to 30 MPa fluid pressures for 2 to 5 days. Two markedly different starting surface textures were used: polished, optically flat surfaces and tensile fracture surfaces. An exploratory experiment also was performed to assess the occurrence of a pressure solution phenomenon on a polished quartzite surface at contact regions of indenting quartz sand grains. Scanning electron microscopy studies indicate progressive increases in the amount of dissolution produced significant changes of surface roughness for both initial surface textures. Surface roughness increased measurably, with the initially polished surfaces exhibiting the more dramatic changes. The pressure solution experiments did not produce definite results, but several surface features are suggestive of dissolution enhancement at load carrying contacts. 9 refs., 10 figs.

  11. Dissolution and characterization of HEV NiMH batteries.

    PubMed

    Larsson, Kristian; Ekberg, Christian; Ødegaard-Jensen, Arvid

    2013-03-01

    Metal recovery is an essential part of the recycling of hybrid electric vehicle battery waste and the first step in a hydrometallurgical treatment is dissolution of the solid material. The properties of separated battery electrode materials were investigated. Focus was put on both the solid waste and then the dissolution behaviour. The cathode contains metallic nickel that remains undissolved when utilizing non-oxidizing conditions such as hydrochloric or sulphuric acid in combination with a low oxygen atmosphere. In these conditions the cathode active electrode material is fully dissolved. Not dissolving the nickel metal saves up to 37% of the acid consumption for the cathode electrode material. In the commonly used case of oxidizing conditions the nickel metal dissolves and a cobalt-rich phase remains undissolved from the cathode active material. For the anode material a complete and rapid dissolution can be achieved at mild conditions with hydrochloric, nitric or sulphuric acid. Optimal parameters for all cases of dissolution was pH 1 with a reaction time of approximately ≥ 20,000 s. PMID:22796014

  12. Premarital Cohabitation and Marital Dissolution: An Examination of Recent Marriages

    ERIC Educational Resources Information Center

    Manning, Wendy D.; Cohen, Jessica A.

    2012-01-01

    An ongoing question remains for family researchers: Why does a positive association between cohabitation and marital dissolution exist when one of the primary reasons to cohabit is to test relationship compatibility? Drawing on recently collected data from the 2006-2008 National Survey of Family Growth, the authors examined whether premarital…

  13. Divorce and Union Dissolution: Reverberations over Three Generations

    ERIC Educational Resources Information Center

    Connidis, Ingrid Arnet

    2003-01-01

    High divorce rates over the past 40 years have affected multiple generations and have long-term consequences for family relationships. This article applies a life course perspective as it explores the reverberation of relationship dissolution beyond the nuclear family. Qualitative data from a study involving 86 adults from 10 three-generation…

  14. Intramolecular Entropy and Size-Dependent Solution Properties of Nanocrystal-Ligands Complexes.

    PubMed

    Yang, Yu; Qin, Haiyan; Peng, Xiaogang

    2016-04-13

    CdSe-stearates nanocrystal-ligands complex as a whole possess strongly temperature- and size-dependent yet well-defined solubility in small organic solvents, which shows little solvent effects as long as the complexes remained intact. A quantitative thermodynamic model is developed to describe such solubility behavior, which differs fundamentally from conventional models for micron colloids. The model reveals that the conformation entropy of the n-alkanoate chain released in dissolution greatly stabilize the colloidal solution but the strong chain-chain interdigitation between adjacent particles in solid diminishes the solubility. These understandings result in "entropic ligands" (see full disclosure in another report (10.1021/acs.nanolett.6b00730)) as the universal means to battle processability challenges of colloidal nanocrystals. PMID:26923516

  15. Thiophene based europium β-diketonate complexes: effect of the ligand structure on the emission quantum yield.

    PubMed

    Freund, Christelle; Porzio, William; Giovanella, Umberto; Vignali, Francesco; Pasini, Mariacecilia; Destri, Silvia; Mech, Agnieszka; Di Pietro, Sebastiano; Di Bari, Lorenzo; Mineo, Placido

    2011-06-20

    The synthesis and the molecular and photophysical characterization, together with solid state and solution structure analysis, of a series of europium complexes based on β-diketonate ligands are reported. The Eu(III) complex emission, specifically its photoluminescence quantum yield (PL-QY), can be tuned by changing ligands which finely modifies the environment of the metal ion. Steady-state and time-resolved emission spectroscopy and overall PL-QY measurements are reported and related to geometrical features observed in crystal structures of some selected compounds. Moreover, paramagnetic NMR, based on the analogous complexes with other lanthanides, are use to demonstrate that there is a significant structural reorganization upon dissolution, which justifies the observed differences in the emission properties between solid and solution states. The energy of the triplet levels of the ligands and the occurrence of nonradiative deactivation processes clearly account for the luminescence efficiencies of the complexes in the series.

  16. Jagged2 acts as a Delta-like Notch ligand during early hematopoietic cell fate decisions

    PubMed Central

    Van de Walle, Inge; De Smet, Greet; Gärtner, Martina; De Smedt, Magda; Waegemans, Els; Vandekerckhove, Bart; Leclercq, Georges; Plum, Jean; Aster, Jon C.; Bernstein, Irwin D.; Guidos, Cynthia J.; Kyewski, Bruno

    2011-01-01

    Notch signaling critically mediates various hematopoietic lineage decisions and is induced in mammals by Notch ligands that are classified into 2 families, Delta-like (Delta-like-1, -3 and -4) and Jagged (Jagged1 and Jagged2), based on structural homology with both Drosophila ligands Delta and Serrate, respectively. Because the functional differences between mammalian Notch ligands were still unclear, we have investigated their influence on early human hematopoiesis and show that Jagged2 affects hematopoietic lineage decisions very similarly as Delta-like-1 and -4, but very different from Jagged1. OP9 coculture experiments revealed that Jagged2, like Delta-like ligands, induces T-lineage differentiation and inhibits B-cell and myeloid development. However, dose-dependent Notch activation studies, gene expression analysis, and promoter activation assays indicated that Jagged2 is a weaker Notch1-activator compared with the Delta-like ligands, revealing a Notch1 specific signal strength hierarchy for mammalian Notch ligands. Strikingly, Lunatic-Fringe– mediated glycosylation of Notch1 potentiated Notch signaling through Delta-like ligands and also Jagged2, in contrast to Jagged1. Thus, our results reveal a unique role for Jagged1 in preventing the induction of T-lineage differentiation in hematopoietic stem cells and show an unexpected functional similarity between Jagged2 and the Delta-like ligands. PMID:21372153

  17. Dissolution of Si in Molten Al with Gas Injection

    NASA Astrophysics Data System (ADS)

    Seyed Ahmadi, Mehran

    Silicon is an essential component of many aluminum alloys, as it imparts a range of desirable characteristics. However, there are considerable practical difficulties in dissolving solid Si in molten Al, because the dissolution process is slow, resulting in material and energy losses. It is thus essential to examine Si dissolution in molten Al, to identify means of accelerating the process. This thesis presents an experimental study of the effect of Si purity, bath temperature, fluid flow conditions, and gas stirring on the dissolution of Si in molten Al, plus the results of physical and numerical modeling of the flow to corroborate the experimental results. The dissolution experiments were conducted in a revolving liquid metal tank to generate a bulk velocity, and gas was introduced into the melt using top lance injection. Cylindrical Si specimens were immersed into molten Al for fixed durations, and upon removal the dissolved Si was measured. The shape and trajectory of injected bubbles were examined by means of auxiliary water experiments and video recordings of the molten Al free surface. The gas-agitated liquid was simulated using the commercial software FLOW-3D. The simulation results provide insights into bubble dynamics and offer estimates of the fluctuating velocities within the Al bath. The experimental results indicate that the dissolution rate of Si increases in tandem with the melt temperature and bulk velocity. A higher bath temperature increases the solubility of Si at the solid/liquid interface, resulting in a greater driving force for mass transfer, and a higher liquid velocity decreases the resistance to mass transfer via a thinner mass boundary layer. Impurities (with lower diffusion coefficients) in the form of inclusions obstruct the dissolution of the Si main matrix. Finally, dissolution rate enhancement was observed by gas agitation. It is postulated that the bubble-induced fluctuating velocities disturb the mass boundary layer, which

  18. A Model for Dissolution of Lime in Steelmaking Slags

    NASA Astrophysics Data System (ADS)

    Sarkar, Rahul; Roy, Ushasi; Ghosh, Dinabandhu

    2016-08-01

    In a previous study by Sarkar et al. (Metall. Mater. Trans. B 46B:961 2015), a dynamic model of the LD steelmaking was developed. The prediction of the previous model (Sarkar et al. in Metall. Mater. Trans. B 46B:961 2015) for the bath (metal) composition matched well with the plant data (Cicutti et al. in Proceedings of 6th International Conference on Molten Slags, Fluxes and Salts, Stockholm City, 2000). However, with respect to the slag composition, the prediction was not satisfactory. The current study aims to improve upon the previous model Sarkar et al. (Metall. Mater. Trans. B 46B:961 2015) by incorporating a lime dissolution submodel into the earlier one. From the industrial point of view, the understanding of the lime dissolution kinetics is important to meet the ever-increasing demand of producing low-P steel at a low basicity. In the current study, three-step kinetics for the lime dissolution is hypothesized on the assumption that a solid layer of 2CaO·SiO2 should form around the unreacted core of the lime. From the available experimental data, it seems improbable that the observed kinetics should be controlled singly by any one kinetic step. Accordingly, a general, mixed control model has been proposed to calculate the dissolution rate of the lime under varying slag compositions and temperatures. First, the rate equation for each of the three rate-controlling steps has been derived, for three different lime geometries. Next, the rate equation for the mixed control kinetics has been derived and solved to find the dissolution rate. The model predictions have been validated by means of the experimental data available in the literature. In addition, the effects of the process conditions on the dissolution rate have been studied, and compared with the experimental results wherever possible. Incorporation of this submodel into the earlier global model (Sarkar et al. in Metall. Mater. Trans. B 46B:961 2015) enables the prediction of the lime dissolution rate

  19. Quartz dissolution: Negative crystal experiments and a rate law

    NASA Astrophysics Data System (ADS)

    Gratz, Andrew J.; Bird, Peter

    1993-03-01

    The negative crystal method is used to extend the range of measured quartz dissolution rates as a function of temperature and pOH, extent of saturation, and ionic strength. The activation energy is constant for pOH = 1 to 4, and rate decreases linearly with saturation, indicating a precipitation reaction that is first order in silicic acid. Dissolution is slowed by Ca and Mg ions; the effect of Ca is strongest on the unit rhombohedra. A simple rate law based on surface charging is proposed and shown to fit the data. Only a reaction in which the activated complex is negatively charged is consistent with rate measurements. Some constraints on fundamental kinetic parameters are inferred. Data for all materials (single crystals and powders) can be fit by the single rate law < Rdiss> = G· A0· T· S·exp(- Ediss/ RT), S = I0.3 · {0.095 · aoH- -0.5+ 1} -1, G = 1 for rough faces while G = Y · exp(- ΔEinter/ RT) for smooth faces, A0 = 6.64 · 10 -3ms s-1K-1, where = limiting dissolution rate in m/s, S is the surface charge, aOH- is the molal hydroxide activity relative to an infinitely dilute solution at STP, I is the ionic strength, T is the temperature, ΔEinter is the energy of interaction ( 6 kJ/mol) causing step formation on the crystal surface, Ediss is the activation energy of dissolution of 78.6 kJ/mol, and Y is a face constant equal to 1 for the prism and 1.63 or 1.87 for the positive and negative unit rhombs, respectively. The available data in the literature suggests G = 1 to 9.5 for various other crystal directions, G = 2-4 for powders with optically estimated areas, while G = 0.1-0.3 describes powders with BET-determined areas. This equation applies over a wide range of conditions: 25-300°C, ionic strength 0.003-0.1 m, and any pOH below the point of zero charge of quartz; a similar equation applies to growth. Dissolution mechanisms for defective crystals are discussed and may result in dissolution rate enhancements of 2X. The observation that

  20. A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

    SciTech Connect

    Chen Zhu

    2006-08-31

    Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory measured and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between laboratory and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO2 injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the second year of the project, we completed CO{sub 2}-Navajo sandstone interaction batch and flow-through experiments and a Navajo sandstone dissolution experiment without the presence of CO{sub 2} at 200 C and 250-300 bars, and initiated dawsonite dissolution and solubility experiments. We also performed additional 5-day experiments at the

  1. Effects of Bacillus subtilis endospore surface reactivity on the rate of forsterite dissolution

    NASA Astrophysics Data System (ADS)

    Harrold, Z.; Gorman-Lewis, D.

    2013-12-01

    Primary mineral dissolution products, such as silica (Si), calcium (Ca) and magnesium (Mg), play an important role in numerous biologic and geochemical cycles including microbial metabolism, plant growth and secondary mineral precipitation. The flux of these and other dissolution products into the environment is largely controlled by the rate of primary silicate mineral dissolution. Bacteria, a ubiquitous component in water-rock systems, are known to facilitate mineral dissolution and may play a substantial role in determining the overall flux of dissolution products into the environment. Bacterial cell walls are complex and highly reactive organic surfaces that can affect mineral dissolution rates directly through microbe-mineral adsorption or indirectly by complexing dissolution products. The effect of bacterial surface adsorption on chemical weathering rates may even outweigh the influence of active processes in environments where a high proportion of cells are metabolically dormant or cell metabolism is slow. Complications associated with eliminating or accounting for ongoing metabolic processes in long-term dissolution studies have made it challenging to isolate the influence of cell wall interactions on mineral dissolution rates. We utilized Bacillus subtilis endospores, a robust and metabolically dormant cell type, to isolate and quantify the effects of bacterial surface reactivity on forsterite (Mg2SiO4) dissolution rates. We measured the influence of both direct and indirect microbe-mineral interactions on forsterite dissolution. Indirect pathways were isolated using dialysis tubing to prevent mineral-microbe contact while allowing free exchange of dissolved mineral products and endospore-ion adsorption. Homogenous experimental assays allowed both direct microbe-mineral and indirect microbe-ion interactions to affect forsterite dissolution rates. Dissolution rates were calculated based on silica concentrations and zero-order dissolution kinetics

  2. [Improvement of dissolution test using micro-controlled roller pump].

    PubMed

    Nagai, Noriaki; Konishi, Nahoko; Nitta, Tadahisa; Taga, Atsushi; Ito, Yoshimasa

    2012-01-01

    The dissolution test is a core performance test in pharmaceutical development and quality control of solid drug products. The conventional HPLC dissolution method (batch-sampling method) involves many steps including the filtration, collection and replenishment of sample solutions. We previously reported a dissolution test that involved microdialysis methods (microdialysis-HPLC method) and allowed many steps to be omitted. However, the recovery rate of theophylline by the microdialysis-HPLC method was lower, and the decrease in the flow rate through the dialysis probe caused variation between each tablet. In this study, we have attempted to improve the dissolution test by using a precise micro-controlled roller pump and microfiltering probe (microfiltering-HPLC method). Sustained release preparations of Theodur (100 mg) were used, and the test solutions used were water, buffer at pH 1.2 and pH 6.8, and pH 6.8-buffer containing 0.1-1% polysorbate 80 or sodium lauryl sulfate. In all test solutions, the microfiltering-HPLC method was able to accomplish continuous sampling of sample solutions, and the recovery rate of theophylline was over 90%. The dissolution behavior by the microfiltering-HPLC method tends to reflect the pharmaceutical design in comparison with the batch-sampling method, and the standard deviations by the microfiltering-HPLC are lower than with the batch-sampling method. In addition, the microfiltering-HPLC method allows many steps to be omitted, such as the filtration, collection and replenishment of sample solutions. These findings provide significant information that can be used in the pharmaceutical development and quality assessment of solid drug products.

  3. Dissolution rates of uranium compounds in simulated lung fluid

    SciTech Connect

    Kalkwarf, D.R.

    1981-01-01

    Maximum dissolution rates of uranium into simulated lung fluid from a variety of materials were measured at 37/sup 0/in the where f/sub i/ is in order to estimate clearance rates from the deep lung. A batch procedure was utilized in which samples containing as little as 10 ..mu..g of natural uranium could be tested. The materials included: products of uranium mining, milling and refining operations, coal fly ash, an environmental sample from a site exposed to multiple uranium sources, and purified samples of (NH/sub 4/)/sub 2/U/sub 2/O/sub 7/ U/sub 3/O/sub 8/, UO/sub 2/, and UF/sub 4/. Dissolution of uranium from several materials indicated the presence of more than one type of uranium compound; but in all cases, the fraction F of uranium remaining undissolved at any time t could be represented by the sum of up to three terms in the series: F = ..sigma../sub i/f/sub i/ exp (-0.693t/UPSILON/sub i/), where f/sub i/ is the initial fraction of component i with dissolution half-time epsilon/sub i/. Values of epsilon/sub i/ varied from 0.01 day to several thousand days depending on the physical and chemical form of the uranium. Dissolution occurred predominantly by formation of the (UO/sub 2/(CO/sub 3/)/sub 3/)/sup 4 -/ ion; and as a result, tetravalent uranium compounds dissolved slowly. Dissolution rates of size-separated yellow-cake aerosols were found to be more closely correlated with specific surface area than with aerodynamic diameter.

  4. Dissolution studies of hydroxyapatite and glass-reinforced hydroxyapatite ceramics

    SciTech Connect

    Queiroz, A.C.; Santos, J.D.; Monteiro, F.J.; Prado da Silva, M.H

    2003-03-15

    In the continuous agitation assays, glass-reinforced hydroxyapatite (GR-HA) was shown to form a calcium phosphate (CaP) layer, but hydroxyapatite (HA) only formed dispersed precipitates. The formation of this layer was first detected on the GR-HA with a 7.5% glass addition (7.5 GR-HA) after only 3 days of immersion in simulated body fluid (SBF). The time required for layer formation decreased as the amount of glass added to the HA increased. The dissolution rate of the materials followed a similar pattern, i.e. the dissolution rate for GR-HA was higher than for HA, and increased with the addition of glass. The immersion of 7.5 GR-HA in water showed almost linear dissolution kinetics over the immersion periods (3, 7, 15, 30 and 60 days). The concentration of calcium ions in solution and the scanning electron microscopy (SEM) analysis of the 7.5 GR-HA specimens immersed in water and in SBF revealed a clear competition between the material dissolution and the precipitation of a CaP phase. Fourier transformed infrared spectroscopy with alternated total reflectance (FTIR-ATR) analysis indicated that the CaP phase that formed during longer immersion times (30 and 60 days) could be a carbonate-substituted CaP precipitate. As expected from previous work, the GR-HA behavior in terms of its in vitro bioactivity is higher than HA because a homogeneous CaP layer is formed and the precipitation occurs faster. From the dissolution test and in accordance with the chemical composition of the samples, GR-HA was more soluble than HA.

  5. Test Objectives for the Saltcake Dissolution Retrieval Demonstration

    SciTech Connect

    DEFIGH PRICE, C.

    2000-09-22

    This document describes the objectives the Saltcake Dissolution Retrieval Demonstration. The near term strategy for single-shell tank waste retrieval activities has shifted from focusing on maximizing the number of tanks entered for retrieval (regardless of waste volume or content) to a focus on scheduling the retrieval of wastes from those single-shell tanks with a high volume of contaminants of concern. These contaminants are defined as mobile, long-lived radionuclides that have a potential of reaching the groundwater and the Columbia River. This strategy also focuses on the performance of key retrieval technology demonstrations, including the Saltcake Dissolution Retrieval Demonstration, in a variety of waste forms and tank farm locations to establish a technical basis for future work. The work scope will also focus on the performance of risk assessment, retrieval performance evaluations (RPE) and incorporating vadose zone characterization data on a tank-by-tank basis, and on updating tank farm closure/post closure work plans. The deployment of a retrieval technology other than Past-Practice Sluicing (PPS) allows determination of limits of technical capabilities, as well as, providing a solid planning basis for future SST retrievals. This saltcake dissolution technology deployment test will determine if saltcake dissolution is a viable retrieval option for SST retrieval. CH2M Hill Hanford Group (CHG) recognizes the SST retrieval mission is key to the success of the River Protection Project (RPP) and the overall completion of the Hanford Site cleanup. The objectives outlined in this document will be incorporated into and used to develop the test and evaluation plan for saltcake dissolution retrievals. The test and evaluation plan will be developed in fiscal year 2001.

  6. Selective Electrocatalytic Activity of Ligand Stabilized Copper Oxide Nanoparticles

    SciTech Connect

    Kauffman, Douglas R; Ohodnicki, Paul R; Kail, Brian W; Matranga, Christopher

    2011-01-01

    Ligand stabilization can influence the surface chemistry of Cu oxide nanoparticles (NPs) and provide unique product distributions for electrocatalytic methanol (MeOH) oxidation and CO{sub 2} reduction reactions. Oleic acid (OA) stabilized Cu{sub 2}O and CuO NPs promote the MeOH oxidation reaction with 88% and 99.97% selective HCOH formation, respectively. Alternatively, CO{sub 2} is the only reaction product detected for bulk Cu oxides and Cu oxide NPs with no ligands or weakly interacting ligands. We also demonstrate that OA stabilized Cu oxide NPs can reduce CO{sub 2} into CO with a {approx}1.7-fold increase in CO/H{sub 2} production ratios compared to bulk Cu oxides. The OA stabilized Cu oxide NPs also show 7.6 and 9.1-fold increases in CO/H{sub 2} production ratios compared to weakly stabilized and non-stabilized Cu oxide NPs, respectively. Our data illustrates that the presence and type of surface ligand can substantially influence the catalytic product selectivity of Cu oxide NPs.

  7. Silver nanoparticle-algae interactions: oxidative dissolution, reactive oxygen species generation and synergistic toxic effects.

    PubMed

    He, Di; Dorantes-Aranda, Juan José; Waite, T David

    2012-08-21

    The short-term toxicity of citrate-stabilized silver nanoparticles (AgNPs) and ionic silver Ag(I) to the ichthyotoxic marine raphidophyte Chattonella marina has been examined using the fluorometric indicator alamarBlue. Aggregation and dissolution of AgNPs occurred after addition to GSe medium while uptake of dissolved Ag(I) occurred in the presence of C. marina. Based on total silver mass, toxicity was much higher for Ag(I) than for AgNPs. Cysteine, a strong Ag(I) ligand, completely removed the inhibitory effects of Ag(I) and AgNPs on the metabolic activity of C. marina, suggesting that the toxicity of AgNPs was due to the release of Ag(I). Synergistic toxic effects of AgNPs/Ag(I) and C. marina to fish gill cells were observed with these effects possibly attributable to enhancement in the generation of reactive oxygen species by C. marina on exposure of the organism to silver.

  8. Expansion of the Ligand Knowledge Base for Chelating P,P-Donor Ligands (LKB-PP).

    PubMed

    Jover, Jesús; Fey, Natalie; Harvey, Jeremy N; Lloyd-Jones, Guy C; Orpen, A Guy; Owen-Smith, Gareth J J; Murray, Paul; Hose, David R J; Osborne, Robert; Purdie, Mark

    2012-08-13

    We have expanded the ligand knowledge base for bidentate P,P- and P,N-donor ligands (LKB-PP, Organometallics2008, 31, 1372-1383) by 208 ligands and introduced an additional steric descriptor (nHe8). This expanded knowledge base now captures information on 334 bidentate ligands and has been processed with principal component analysis (PCA) of the descriptors to produce a detailed map of bidentate ligand space, which better captures ligand variation and has been used for the analysis of ligand properties. PMID:24882917

  9. Change in surface area and dissolution rates during hornblende dissolution at pH 4.0

    NASA Astrophysics Data System (ADS)

    Zhang, Hailin; Bloom, Paul R.; Nater, Edward A.

    1993-04-01

    Four particle-size fractions (0.045-0.075, 0.075-0.11, 0.11-0.25, and 0.50-1.00 mm sieve sizes) were used to study the relationships of bulk dissolution rates (mol g -1s -1) to particle size and measured specific surface area. All reactions were performed on sonically cleaned samples in pH 4.0, 0.01 M HOAc-LiOAc buffer at 298 K. To minimize the effects of grinding, dissolution rates were not determined until 30 days of weathering had occurred; subsequent bulk dissolution rates were still nonlinear with time and the reaction was incongruent. Bulk reaction rates were higher for the smaller particle size fractions. The rates of release of Al, Fe, and Mg were first order with respect to surface area, but the order of release for Si was 0.39. These results suggest that the direct relationship between the quantity of exposed crystalline defects and dissolution rates suggested by previous investigators does not hold true for hornblende. The surface area of hornblende grains increased 99% on average during the first 30 days of weathering, and an additional 12% during the next 29 days of weathering. Scanning electron micrographs and N 2 adsorption-desorption isotherms (77 K) indicated that the formation of etch pits and hollow dissolution cores contributed to the increased surface area. High resolution TEM observations of surface materials removed by ultrasonic treatment and N 2 adsorption hysteresis data suggest weathering along cleavage planes with the formation of 0.5-13 nm pores. Most of the increased adsorption of N 2 in the surface area determinations, however, was due to the formation of larger etch features.

  10. Nanosuspensions Containing Oridonin/HP-β-Cyclodextrin Inclusion Complexes for Oral Bioavailability Enhancement via Improved Dissolution and Permeability.

    PubMed

    Zhang, Xingwang; Zhang, Tianpeng; Lan, Yali; Wu, Baojian; Shi, Zhihai

    2016-04-01

    Chemotherapy via oral route of anticancer drugs offers much convenience and compliance to patients. However, oral chemotherapy has been challenged by limited absorption due to poor drug solubility and intestinal efflux. In this study, we aimed to develop a nanosuspension formulation of oridonin (Odn) using its cyclodextrin inclusion complexes to enhance oral bioavailability. Nanosuspensions containing Odn/2 hydroxypropyl-β-cyclodextrin inclusion complexes (Odn-CICs) were prepared by a solvent evaporation followed by wet media milling technique. The nanosuspensions were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and dissolution. The resulting nanosuspensions were approximately 313.8 nm in particle size and presented a microcrystal morphology. Nanosuspensions loading Odn-CICs dramatically enhanced the dissolution of Odn. Further, the intestinal effective permeability of Odn was markedly enhanced in the presence of 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) and poloxamer. Bioavailability studies showed that nanosuspensions with Odn-CICs can significantly promote the oral absorption of Odn with a relative bioavailability of 213.99% (Odn suspensions as reference). Odn itself possesses a moderate permeability and marginal intestinal metabolism. Thus, the enhanced bioavailability for Odn-CIC nanosuspensions can be attributed to improved dissolution and permeability by interaction with absorptive epithelia and anti-drug efflux. Nanosuspensions prepared from inclusion complexes may be a promising approach for the oral delivery of anticancer agents.

  11. Repassivation behavior of 316L stainless steel in borate buffer solution: Kinetics analysis of anodic dissolution and film formation

    NASA Astrophysics Data System (ADS)

    Xu, Haisong; Sun, Dongbai; Yu, Hongying

    2015-12-01

    The repassivation behavior of metals or alloys after oxide film damage determines the development of local corrosion and corrosion resistance. In this work, the repassivation kinetics of 316L stainless steel (316L SS) are investigated in borate buffer solution (pH 9.1) by using the abrading electrode technique. The current densities flowing from bare 316L SS surface are measured by potentiostatic method and analyzed to characterize repassivation kinetics. The initial stages of current decay (t < 500 ms) are discussed according to a film growth model, which describes the initial current transient should be divided into substrate dissolution current and passive film formation current based on Avrami kinetics. Then the two independent components are analyzed individually. The film formation rate and the thickness of film are compared in different applied potential. It is shown that anodic dissolution dominates the repassivation for a short time during the early times, and a higher applied potential will promote the anodic dissolution of metal. The film growth rate increases slightly with increasing in potential. Correspondingly, increase in applied potential from 0 VSCE to 0.8 VSCE results in thicker monolayer, which covers the whole bare surface at the time of θ = 1. The electric field strengths through the thin passive film could reach 3.97 × 106 V cm-1.

  12. EVALUATION OF LOW TEMPERATURE ALUMINUM DISSOLUTION IN TANK 51

    SciTech Connect

    Pike, J

    2008-09-04

    Liquid Waste Organization (LWO) identified aluminum dissolution as a method to mitigate the effect of having about 50% more solids in High Level Waste (HLW) sludge than previously planned. Previous aluminum dissolution performed in a HLW tank in 1982 was performed at approximately 85 C for 5 days, which became the baseline aluminum dissolution process. LWO initiated a project to modify a waste tank to meet these requirements. Subsequent to an alternative evaluation, LWO management identified an opportunity to perform aluminum dissolution on sludge destined for Sludge Batch 5, but within a limited window that would not allow time for any modifications for tank heating. A variation of the baseline process, dubbed Low Temperature Aluminum Dissolution (LTAD), was developed based on the constraint of available energy input in Tank 51 and the window of opportunity, but was not constrained to a minimum extent of dissolution, i.e. dissolve as much aluminum as possible within the time available. This process was intended to operate between 55 and 70 C, but for a significantly longer time than the baseline process. LTAD proceeded in parallel with the baseline project. The preliminary evaluation at the completion of LTAD focused on the material balance and extent of the aluminum dissolved. The range of values of extent of dissolution, 56% to 64%, resulted from the variation in liquid phase sample data available at the time. Additional solid phase data is available from a sample taken after LTAD to refine this range. This report provides additional detailed evaluation of the LTAD process based on analytical and field data and includes: a summary of the process chronology; a determination of an acceptable blending strategy for the aluminum-laden supernate stored in Tank 11; an update to the determination of aluminum dissolved using more complete sample results; a determination of the effect of LTAD on uranium, plutonium, and other metals; a determination of the rate of heat

  13. Dissolution on Titan and on Earth: Towards the age of Titan's karstic landscapes

    NASA Astrophysics Data System (ADS)

    Cornet, T.; Cordier, D.; Le Bahers, T.; Bourgeois, O.; Fleurant, C.; Le Mouélic, S.; Altobelli, N.

    2015-10-01

    The morphology of Titan's lacustrine depressions led to comparisons with terrestrial depressions developed by karstic dissolution. We tested this hypothesis by computing dissolution rates of Titan's solids in liquid methane. We inferred from these rates the timescales needed to create dissolution landforms of a given depth. Dissolution would be a very efficient geological process to shape Titan's surface, on timescales generally shorter than 100 Myrs, consistent with the youth of Titan's surface (<1 Gyr).

  14. Characterization of phagolysosomal simulant fluid for study of beryllium aerosol particle dissolution.

    PubMed

    Stefaniak, A B; Guilmette, R A; Day, G A; Hoover, M D; Breysse, P N; Scripsick, R C

    2005-02-01

    A simulant of phagolysosomal fluid is needed for beryllium particle dissolution research because intraphagolysosomal dissolution is believed to be a necessary step in the cellular immune response associated with development of chronic beryllium disease. Thus, we refined and characterized a potassium hydrogen phthalate (KHP) buffered solution with pH 4.55, termed phagolysosomal simulant fluid (PSF), for use in a static dissolution technique. To characterize the simulant, beryllium dissolution in PSF was compared to dissolution in the J774A.1 murine cell line. The effects of ionic composition, buffer strength, and the presence of the antifungal agent alkylbenzyldimethylammonium chloride (ABDC) on beryllium dissolution in PSF were evaluated. Beryllium dissolution in PSF was not different from dissolution in the J774A.1 murine cell line (p = 0.78) or from dissolution in another simulant having the same pH but different ionic composition (p = 0.73). A buffer concentration of 0.01-M KHP did not appear adequate to maintain pH under all conditions. There was no difference between dissolution in PSF with 0.01-M KHP and 0.02-M KHP (p = 0.12). At 0.04-M KHP, beryllium dissolution was increased relative to 0.02-M KHP (p = 0.02). Use of a 0.02-M KHP buffer concentration in the standard formulation for PSF provided stability in pH without alteration of the dissolution rate. The presence of ABDC did not influence beryllium dissolution in PSF (p = 0.35). PSF appears to be a useful and appropriate model of in vitro beryllium dissolution when using a static dissolution technique. In addition, the critical approach used to evaluate and adjust the composition of PSF may serve as a framework for characterizing PSF to study dissolution of other metal and oxide particles.

  15. Controlled-deactivation cannabinergic ligands.

    PubMed

    Sharma, Rishi; Nikas, Spyros P; Paronis, Carol A; Wood, Jodianne T; Halikhedkar, Aneetha; Guo, Jason Jianxin; Thakur, Ganesh A; Kulkarni, Shashank; Benchama, Othman; Raghav, Jimit Girish; Gifford, Roger S; Järbe, Torbjörn U C; Bergman, Jack; Makriyannis, Alexandros

    2013-12-27

    We report an approach for obtaining novel cannabinoid analogues with controllable deactivation and improved druggability. Our design involves the incorporation of a metabolically labile ester group at the 2'-position on a series of (-)-Δ(8)-THC analogues. We have sought to introduce benzylic substituents α to the ester group which affect the half-lives of deactivation through enzymatic activity while enhancing the affinities and efficacies of individual ligands for the CB1 and CB2 receptors. The 1'-(S)-methyl, 1'-gem-dimethyl, and 1'-cyclobutyl analogues exhibit remarkably high affinities for both CB receptors. The novel ligands are susceptible to enzymatic hydrolysis by plasma esterases in a controllable manner, while their metabolites are inactive at the CB receptors. In further in vitro and in vivo experiments key analogues were shown to be potent CB1 receptor agonists and to exhibit CB1-mediated hypothermic and analgesic effects.

  16. Presentation of Ligands on Hydroxylapatite

    NASA Technical Reports Server (NTRS)

    Chu, Barbara C. F.; Orgel, Leslie E.

    1997-01-01

    Conjugates of biotin with the decamer of glutamic acid (glu(sub 10)) and the trimer of D,L-2-amino-5-phosphonovaleric acid (I) have been synthesized, and it has been shown that they mediate the binding of avidin to hydroxylapatite. In a similar way a conjugate of methotrexate with glu(sub 10) mediates the binding of dihydrofolate reductase to the mineral. The presentation of ligands on the hydroxylapatite component of bone may find applications in clinical medicine.

  17. Unusual ligand coordination for cesium

    SciTech Connect

    Bryan, J.C.; Kavallieratos, K.; Sachleben, R.A.

    2000-04-03

    When complexed by tetrabenzo-24-crown-8, the cesium ion can accommodate unprecedented ligation. The structures of the complexes are presented. These structures are the first reported examples of linear {eta}{sup 2}-acetonitrile coordination to any metal ion and the first structures illustrating {eta}{sup 2}-acetonitrile and dichloromethane ligation to an alkali metal ion. Possible steric and electronic origins of these unusual metal-ligand interactions are discussed.

  18. Absolute Ligand Discrimination by Dimeric Signaling Receptors.

    PubMed

    Fathi, Sepehr; Nayak, Chitra R; Feld, Jordan J; Zilman, Anton G

    2016-09-01

    Many signaling pathways act through shared components, where different ligand molecules bind the same receptors or activate overlapping sets of response regulators downstream. Nevertheless, different ligands acting through cross-wired pathways often lead to different outcomes in terms of the target cell behavior and function. Although a number of mechanisms have been proposed, it still largely remains unclear how cells can reliably discriminate different molecular ligands under such circumstances. Here we show that signaling via ligand-induced receptor dimerization-a very common motif in cellular signaling-naturally incorporates a mechanism for the discrimination of ligands acting through the same receptor. PMID:27602720

  19. Ligand substitution behavior of Ru6(mu6-C)(CO)17 with unsaturated diphosphines: facile capping of a polyhedral face and photochemically promoted P C bond cleavage in the cluster Ru6(mu6-C)(CO)14(mu3-bpcd)

    SciTech Connect

    Kandala, Srikanth; Hammons, Casey; Watson, William H.; Wang, Xiaoping; Richmond, Michael G.

    2010-01-01

    The ligand substitution chemistry of the hexaruthenium cluster Ru-6(mu(6)-C)(CO)(17) (1) with several unsaturated diphosphine ligands has been investigated. Thermolysis of 1 with (Z)-Ph2PCH=CHPPh2 (dppen) furnishes the new cluster compounds Ru-5(mu(5)-C)(CO)(12)(mu(3)-dppen) (2), Ru-6(mu(6)-C)(CO)(14)(mu(3)-dppen) (3), and Ru-6(mu(6)-C)(CO)(12)(mu(3)-dppen)(mu-dppen) (4). Clusters 2 and 3 are also obtained when a mixture of 1 and dppen is treated with the oxidative-decarbonylation reagent Me3NO. Thermolysis or Me3NO activation of 1 in the presence of 4,5-bis(diphenylphosphino)-4-cyclopenten- 1,3-dione (bpcd) yields Ru-6(mu(6)-C)(CO)(14)(mu(3)-bpcd) (4) as the sole observable product. Near-UV irradiation of 4 leads to P-C bond cleavage and the formation of phosphido-bridged cluster Ru-6(mu(6)-C)(CO)(13)[mu(3)-C=C(PPh2)C(O)CH2C(O)](mu-PPh2) (6) in essentially quantitative yield. The reaction between 1 and the ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) leads to the formation of Ru-6(mu(6)-C)(CO)(14)(mu(3)-bmf) (7), which exists as a single diastereomer in solution as shown by H-1 and P-31 NMR spectroscopy. The molecular structures and the binding mode of the ancillary diphosphine ligand(s) in 2-7 have all been established by X-ray diffraction analyses. The solid-state structure of 7 reveals that the chiral bmf ligand caps one of the metallic faces stereospecifically with the 5-methoxy moiety oriented distal or trans relative to the Ru-6 polyhedral core. The new substitution products are discussed relative to the products obtained from 1 and the related diphosphine ligands dppm, dppe, dppf, and dppbz.

  20. Dissolution kinetics of a three-component solid II: benzoic acid, salicylic acid, and salicylamide.

    PubMed

    Parrott, E L; Simpson, M; Flanagan, D R

    1983-07-01

    The dissolution rates of each component in compressed spheres consisting of three components were measured under sink conditions. The observed dissolution rates of benzoic acid, salicylic acid, and salicylamide compare favorably to the predicted dissolution rates according to a previously presented kinetic model.

  1. In situ dissolution analysis using coherent anti-Stokes Raman scattering (CARS) and hyperspectral CARS microscopy.

    PubMed

    Fussell, Andrew; Garbacik, Erik; Offerhaus, Herman; Kleinebudde, Peter; Strachan, Clare

    2013-11-01

    The solid-state form of an active pharmaceutical ingredient (API) in an oral dosage form plays an important role in determining the dissolution rate of the API. As the solid-state form can change during dissolution, there is a need to monitor the oral dosage form during dissolution testing. Coherent anti-Stokes Raman scattering (CARS) microscopy provides rapid, spectrally selective imaging to monitor the oral dosage form during dissolution. In this study, in situ CARS microscopy was combined with inline UV absorption spectroscopy to monitor the solid-state change in oral dosage forms containing theophylline anhydrate undergoing dissolution and to correlate the solid-state change with a change in dissolution rate. The results from in situ CARS microscopy showed that theophylline anhydrate converted to theophylline monohydrate during dissolution resulting in a reduction in the dissolution rate. The addition of methyl cellulose to the dissolution medium was found to delay the theophylline monohydrate growth and changed the morphology of the monohydrate. The net effect was an increased dissolution rate for theophylline anhydrate. Our results show that in situ CARS microscopy combined with inline UV absorption spectroscopy is capable of monitoring oral dosage forms undergoing dissolution and correlating changes in solid-state form with changes in dissolution rate. PMID:23994672

  2. 15 CFR 295.23 - Dissolution of joint research and development ventures.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... Development Ventures § 295.23 Dissolution of joint research and development ventures. Upon dissolution of any joint research and development venture receiving funds under these procedures or at a time otherwise... 15 Commerce and Foreign Trade 1 2010-01-01 2010-01-01 false Dissolution of joint research...

  3. Dissolution rates of coals and graphite in Fe-C-S melts in direct ironmaking: Dependence of carbon dissolution rate on carbon structure

    SciTech Connect

    Wu, C.; Sahajwalla, V.

    2000-02-01

    It is commonly recognized that the rates of carbon dissolution from graphite as compared to that from glassy carbon are very different, although they are similar in composition and density. Previous studies have established that the liquid-side mass-transfer rate limitation mechanism could not account for the carbon dissolution from nongraphite carbon sources. It has been assumed that the carbon structure affects its dissolution rate in molten iron. In many in-bath direct smelting processes such as HISMELT, predicting the carbon dissolution rate of coals prior to their use in a smelting bath is crucial. In order to verify the relationship between the carbon dissolution rate and the structure of coals, carbon dissolution experiments were conducted in an induction to furnace using the carburizer cover method.

  4. Secretory pathways generating immunosuppressive NKG2D ligands

    PubMed Central

    Baragaño Raneros, Aroa; Suarez-Álvarez, Beatriz; López-Larrea, Carlos

    2014-01-01

    Natural Killer Group 2 member D (NKG2D) activating receptor, present on the surface of various immune cells, plays an important role in activating the anticancer immune response by their interaction with stress-inducible NKG2D ligands (NKG2DL) on transformed cells. However, cancer cells have developed numerous mechanisms to evade the immune system via the downregulation of NKG2DL from the cell surface, including the release of NKG2DL from the cell surface in a soluble form. Here, we review the mechanisms involved in the production of soluble NKG2DL (sNKG2DL) and the potential therapeutic strategies aiming to block the release of these immunosuppressive ligands. Therapeutically enabling the NKG2D-NKG2DL interaction would promote immunorecognition of malignant cells, thus abrogating disease progression. PMID:25050215

  5. Ligand regulation of a constitutively dimeric EGF receptor

    NASA Astrophysics Data System (ADS)

    Freed, Daniel M.; Alvarado, Diego; Lemmon, Mark A.

    2015-06-01

    Ligand-induced receptor dimerization has traditionally been viewed as the key event in transmembrane signalling by epidermal growth factor receptors (EGFRs). Here we show that the Caenorhabditis elegans EGFR orthologue LET-23 is constitutively dimeric, yet responds to its ligand LIN-3 without changing oligomerization state. SAXS and mutational analyses further reveal that the preformed dimer of the LET-23 extracellular region is mediated by its domain II dimerization arm and resembles other EGFR extracellular dimers seen in structural studies. Binding of LIN-3 induces only minor structural rearrangements in the LET-23 dimer to promote signalling. Our results therefore argue that EGFR can be regulated by allosteric changes within an existing receptor dimer--resembling signalling by insulin receptor family members, which share similar extracellular domain compositions but form covalent dimers.

  6. Ligand identification using electron-density mapcorrelations

    SciTech Connect

    Terwilliger, Thomas C.; Adams, Paul D.; Moriarty, Nigel W.; Cohn,Judith D.

    2006-12-01

    A procedure for the identification of ligands bound incrystal structuresof macromolecules is described. Two characteristics ofthe density corresponding to a ligand are used in the identificationprocedure. One is the correlation of the ligand density with each of aset of test ligands after optimization of the fit of that ligand to thedensity. The other is the correlation of a fingerprint of the densitywith the fingerprint of model density for each possible ligand. Thefingerprints consist of an ordered list of correlations of each the testligands with the density. The two characteristics are scored using aZ-score approach in which the correlations are normalized to the mean andstandard deviation of correlations found for a variety of mismatchedligand-density pairs, so that the Z scores are related to the probabilityof observing a particular value of the correlation by chance. Theprocedure was tested with a set of 200 of the most commonly found ligandsin the Protein Data Bank, collectively representing 57 percent of allligands in the Protein Data Bank. Using a combination of these twocharacteristics of ligand density, ranked lists of ligand identificationswere made for representative (F-o-F-c) exp(i phi(c)) difference densityfrom entries in the Protein Data Bank. In 48 percent of the 200 cases,the correct ligand was at the top of the ranked list of ligands. Thisapproach may be useful in identification of unknown ligands in newmacromolecular structures as well as in the identification of whichligands in a mixture have bound to a macromolecule.

  7. Stability of core/shell quantum dots--role of pH and small organic ligands.

    PubMed

    Domingos, Rute F; Franco, Cristiana; Pinheiro, José P

    2013-07-01

    The improvement of knowledge about the toxicity and even processability, and stability of quantum dots (QD) requires the understanding of the relationship between the QD binding head group, surface structure, and interligand interaction. The scanned stripping chronopotentiometry and absence of gradients and Nernstian equilibrium stripping techniques were used to determine the concentration of Cd dissolved from a polyacrylate-stabilized CdTe/CdS QD. The effects of various concentrations of small organic ligands such as citric acid, glycine, and histidine and the roles of pH (4.5-8.5) and exposure time (0-48 h) were evaluated. The highest QD dissolution was obtained at the more acidic pH in absence of the ligands (52%) a result of the CdS shell solubility. At pH 8.5 the largest PAA ability to complex the dissolved Cd leads to a further QD solubility until the equilibrium is reached (24% of dissolved Cd vs. 4% at pH 6.0). The citric acid presence resulted in greater QD dissolution, whereas glycine, an amino acid, acts against QD dissolution. Surprisingly, the presence of histidine, an amino acid with an imidazole functional group, leads to the formation of much strong Cd complexes over time, which may be non-labile, inducing variations in the local environment of the QD surface.

  8. Nonaqueous Phase Liquid Dissolution in Porous Media: Multi-Scale Effects of Multi-Component Dissolution Kinetics on Cleanup Time

    SciTech Connect

    McNab, W; Ezzedine, S; Detwiler, R

    2007-02-26

    Industrial organic solvents such as trichloroethylene (TCE) and tetrachloroethylene (PCE) constitute a principal class of groundwater contaminants. Cleanup of groundwater plume source areas associated with these compounds is problematic, in part, because the compounds often exist in the subsurface as dense nonaqueous phase liquids (DNAPLs). Ganglia (or 'blobs') of DNAPL serve as persistent sources of contaminants that are difficult to locate and remediate (e.g. Fenwick and Blunt, 1998). Current understanding of the physical and chemical processes associated with dissolution of DNAPLs in the subsurface is incomplete and yet is critical for evaluating long-term behavior of contaminant migration, groundwater cleanup, and the efficacy of source area cleanup technologies. As such, a goal of this project has been to contribute to this critical understanding by investigating the multi-phase, multi-component physics of DNAPL dissolution using state-of-the-art experimental and computational techniques. Through this research, we have explored efficient and accurate conceptual and numerical models for source area contaminant transport that can be used to better inform the modeling of source area contaminants, including those at the LLNL Superfund sites, to re-evaluate existing remediation technologies, and to inspire or develop new remediation strategies. The problem of DNAPL dissolution in natural porous media must be viewed in the context of several scales (Khachikian and Harmon, 2000), including the microscopic level at which capillary forces, viscous forces, and gravity/buoyancy forces are manifested at the scale of individual pores (Wilson and Conrad, 1984; Chatzis et al., 1988), the mesoscale where dissolution rates are strongly influenced by the local hydrodynamics, and the field-scale. Historically, the physico-chemical processes associated with DNAPL dissolution have been addressed through the use of lumped mass transfer coefficients which attempt to quantify the

  9. Model of heterogeneous material dissolution in simulated biological fluid

    NASA Astrophysics Data System (ADS)

    Knyazeva, A. G.; Gutmanas, E. Y.

    2015-11-01

    In orthopedic research, increasing attention is being paid to bioresorbable/biodegradable implants as an alternative to permanent metallic bone healing devices. Biodegradable metal based implants possessing high strength and ductility potentially can be used in load bearing sites. Biodegradable Mg and Fe are ductile and Fe possess high strength, but Mg degrades too fast and Fe degrades too slow, Ag is a noble metal and should cause galvanic corrosion of the more active metallic iron - thus, corrosion of Fe can be increased. Nanostructuring should results in higher strength and can result in higher rate of dissolution/degradation from grain boundaries. In this work, a simple dissolution model of heterogeneous three phase nanocomposite material is considered - two phases being metal Fe and Ag and the third - nanopores. Analytical solution for the model is presented. Calculations demonstrate that the changes in the relative amount of each phase depend on mass exchange and diffusion coefficients. Theoretical results agree with preliminary experimental results.

  10. Biological Impact of Bioactive Glasses and Their Dissolution Products.

    PubMed

    Hoppe, Alexander; Boccaccini, Aldo R

    2015-01-01

    For many years, bioactive glasses (BGs) have been widely considered for bone tissue engineering applications due to their ability to bond to hard as well as soft tissue (a property termed bioactivity) and for their stimulating effects on bone formation. Ionic dissolution products released during the degradation of the BG matrix induce osteogenic gene expression leading to enhanced bone regeneration. Recently, adding bioactive metallic ions (e.g. boron, copper, cobalt, silver, zinc and strontium) to silicate (or phosphate and borate) glasses has emerged as a promising route for developing novel BG formulations with specific therapeutic functionalities, including antibacterial, angiogenic and osteogenic properties. The degradation behaviour of BGs can be tailored by adjusting the glass chemistry making these glass matrices potential carrier systems for controlled therapeutic ion release. This book chapter summarises the fundamental aspects of the effect of ionic dissolution products from BGs on osteogenesis and angiogenesis, whilst discussing novel BG compositions with controlled therapeutic ion release. PMID:26201273

  11. CO2 dissolution in water using long serpentine microchannels

    PubMed Central

    Cubaud, Thomas; Sauzade, Martin; Sun, Ruopeng

    2012-01-01

    The evolution of carbon dioxide bubbles dissolving in water is experimentally examined using long microchannels. We study the coupling between bubble hydrodynamics and dissolution in confined geometries. The gas impregnation process in liquid produces significant flow rearrangements. Depending on the initial volumetric liquid fraction, three operating regimes are identified, namely saturating, coalescing, and dissolving. The morphological and dynamical transition from segmented to dilute bubbly flows is investigated. Tracking individual bubbles along the flow direction is used to calculate the temporal evolution of the liquid volumetric fraction and the average flow velocity near reference bubbles over long distances. This method allows us to empirically establish the functional relationship between bubble size and velocity. Finally, we examine the implication of this relationship during the coalescing flow regime, which limits the efficiency of the dissolution process. PMID:22655006

  12. Dissolution Kinetics of Solids: Application with Spherical Candy

    NASA Astrophysics Data System (ADS)

    Beauchamp, Guy

    2001-04-01

    This economical and safe kinetics experiment involves the rate of dissolution of a spherical candy in water. The 2/3 order with respect to the measured mass gives students a practical example of a non-integer order usually only encountered in textbooks in free radical processes. Insight is given to the fact that in a dissolving solid sphere, the radius recedes at constant speed. This experiment also may be useful as an introduction to the concepts of solubility and diffusion in a general chemistry course. Temperature dependence on dissolution rate constants revealed an energy of activation of 23 kJ/mol (±1 kJ/mol) for different hard candies.

  13. Degradation and dissolution of hemicelluloses during bamboo hydrothermal pretreatment.

    PubMed

    Ma, X J; Yang, X F; Zheng, X; Lin, L; Chen, L H; Huang, L L; Cao, S L

    2014-06-01

    To elucidate the hemicelluloses degradation and dissolution during hydrothermal pretreatment, hemicelluloses separated from both hydrolysate and pretreated substrate were investigated. Along with the pretreatment proceeding, some hemicelluloses fractions dissolved and diffused into the bulk liquor; MW (molecular weight) of these hemicelluloses fractions increased first and then decreased as well as amount of the fractions. Based on the definition of MW of the soluble hemicellulose, it has been concluded that some insoluble hemicellulose fractions appeared in the hydrolysate. In contrast, the hemicellulose degradation occurred continually and had been observed by the gradual decrease of MW of the hemicellulose isolated from pretreated substrate. Lingering dissolution at the later stage might attribute to the facts that some soluble fractions were still entrapped in the substrate. 5-15% hemicellulose fractions remained in the pretreated substrate at the later stage were composed of soluble species.

  14. Interactions between sparfloxacin and antacids - dissolution and adsorption studies.

    PubMed

    Hussain, Fida; Arayne, M Saeed; Sultana, Najma

    2006-01-01

    Sparfloxacin is a broad-spectrum oral fluoroquinolone antimicrobial agent with a long elimination half-life, extensively used against both Gram-positive as well as Gram-negative microorganism. Concurrent administration of antacids and sparfloxacin decreases the gastrointestinal absorption of sparfloxacin and therapeutic failure may result. The present study was designed to evaluate the influence of some antacids on the availability of sparfloxacin. The release of sparfloxacin from tablets in the presence of antacids like sodium bicarbonate, calcium hydroxide, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, magnesium trisilicate and magaldrate has been studied on BP 2003 dissolution test apparatus. These studies were carried out in simulated gastric and intestinal juices for three hours at 37 degrees C. The results confirmed that the dissolution rate of tablets was markedly retarded in the presence all of antacids studied, whereas magaldrate and calcium carbonate exhibited relatively higher adsorption capacities in simulated gastric juice and magnesium trisilicate and calcium hydroxide in simulated intestinal juice.

  15. HB-Line Dissolution of Glovebox Floor Sweepings

    SciTech Connect

    Gray, J.H.

    1998-02-01

    Two candidate flowsheets for dissolving glovebox floor sweepings in the HB-Line Phase I geometrically favorable dissolver have been developed.Dissolving conditions tested and modified during the laboratory program were based on the current processing scheme for dissolving high-fired Pu-238 oxide in HB-Line. Subsequent adjustments made to the HB-Line flowsheet reflected differences in the dissolution behavior between high-fired Pu-238 oxide and the MgO sand/PuF{sub 4}/PuO{sub 2} mixture in glovebox floor sweepings. Although both candidate flowsheets involved two separate dissolving steps and resulted incomplete dissolution of all solids, the one selected for use in HB-Line will require fewer processing operations and resembles the initial flowsheet proposed for dissolving sand, slag, and crucible material in F-Canyon dissolvers. Complete dissolution of glovebox floor sweepings was accomplished in the laboratory by initially dissolving between 55 and 65{degree} in a 14 molar nitric acid solution. Under these conditions, partial dissolution of PuF{sub 4} and complete dissolution of PuO{sub 2} and MgO sand were achieved in less than one hour. The presence of free fluoride in solution,uncomplexed by aluminum, was necessary for complete dissolution of the PuO{sub 2}.The remaining PuF{sub 4} dissolved following addition of aluminum nitrate nonahydrate (ANN) to complex the fluoride and heating between 75 and 85{degree}C for an additional hour. Precipitation of magnesium and/or aluminum nitrates could occur before, during, and after transfer of product solutions. Both dilution and/or product solution temperature controls may be necessary to prevent precipitation of these salts. Corrosion of the dissolver should not be an issue during these dissolving operations. Corrosion is minimized when dissolving at 55-65{degree}C for one to three hours at a maximum uncomplexed free fluoride concentration of 0.07 molar and by dissolving at 75-85{degree}C at a one to one aluminum to

  16. Brief overview on cellulose dissolution/regeneration interactions and mechanisms.

    PubMed

    Medronho, Bruno; Lindman, Björn

    2015-08-01

    The development of cellulose dissolution/regeneration strategies constitutes an increasingly active research field. These are fundamental aspects of many production processes and applications. A wide variety of suitable solvents for cellulose is already available. Nevertheless, most solvent systems have important limitations, and there is an intense activity in both industrial and academic research aiming to optimize existing solvents and develop new ones. Cellulose solvents are of highly different nature giving great challenges in the understanding of the subtle balance between the different interactions. Here, we briefly review the cellulose dissolution and regeneration mechanisms for some selected solvents. Insolubility is often attributed to strong intermolecular hydrogen bonding between cellulose molecules. However, recent work rather emphasizes the role of cellulose charge and the concomitant ion entropy effects, as well as hydrophobic interactions.

  17. Surface engineering of bismuth nanocrystals to counter dissolution.

    PubMed

    Chakravarty, Shatadru; Unold, Jason; Shuboni-Mulligan, Dorela D; Blanco-Fernandez, Barbara; Shapiro, Erik M

    2016-07-21

    Rapid dissolution of Bi Nanocrystals (NCs) in lysosomal conditions results in poor biocompatibility. We report that an in situ surface coating of Bi nanocrystals with Ganex® V216, a cosmetic dispersant, limits its dissolution under physiological conditions. These Bi Ganex (BiG) NCs are readily encapsulated in FDA approved polymer poly(dl-lactic-co-glycolic acid) (PLGA) by an oil-in-water emulsion technique and also undergo facile SiO2 coating. BiG NCs in BiG@PLGA and BiG@SiO2 nanoparticles dissolve slowly under physiological conditions and exhibit excellent biocompatibility, as opposed to uncoated Bi NCs. Finally, these Bi nanoconstructs are shown to be strong CT CAs, even at relatively low Bi concentrations. PMID:27356280

  18. Dissolution of Spent Nuclear Fuel in Carbonate-Peroxide Solution

    SciTech Connect

    Soderquist, Chuck Z.; Hanson, Brady D.

    2010-01-31

    This study shows that spent UO2 fuel can be completely dissolved in a carbonate-peroxide solution apparently without attacking the metallic Mo-Tc-Ru-Rh-Pd fission product phase. Samples of spent nuclear fuel were pulverized and sieved to a uniform size, then duplicate aliquots were weighed into beakers for analysis. One set was dissolved in near-boiling 10M nitric acid, and the other set was dissolved in a solution of ammonium carbonate and hydrogen peroxide at room temperature. All the resulting fuel solutions were then analyzed for Sr-90, Tc-99, Cs-137, plutonium, and Am-241. For all the samples, the concentrations of Cs-137, Sr-90, plutonium, and Am-241 were the same for both the nitric acid dissolution and the ammonium carbonate-hydrogen peroxide dissolution, but the technetium concentration of the ammonium carbonate-hydrogen peroxide fuel solution was only about 25% of the same fuels dissolved in hot nitric acid.

  19. Dissolution of alkaline earth sulfates in the presence of montmorillonite

    USGS Publications Warehouse

    Eberl, D.D.; Landa, E.R.

    1985-01-01

    In a study of the effect of montmorillonite on the dissolution of BaSO4 (barite), SrSO4 (celestite), and 226Ra from U mill tailings, it was found that: (1) More of these substances dissolve in an aqueous system that contains montmorillonite than dissolve in a similar system without clay, due to the ion exchange properties of the clay; (2) Na-montmorillonite is more effective in aiding dissolution than is Ca-montmorillonite; (3) the amount of Ra that moves from mill tailings to an exchanger increases as solution sulfate activity decreases. Leaching experiments suggest that 226Ra from H2SO4-circuit U mill tailings from Edgemont, South Dakota, is not present as pure Ra sulfate or as an impurity in anhydrite or gypsum; it is less soluble, and probably occurs as a trace constituent in barite.

  20. Spiking Neural P Systems with Neuron Division and Dissolution

    PubMed Central

    Liu, Xiyu; Wang, Wenping

    2016-01-01

    Spiking neural P systems are a new candidate in spiking neural network models. By using neuron division and budding, such systems can generate/produce exponential working space in linear computational steps, thus provide a way to solve computational hard problems in feasible (linear or polynomial) time with a “time-space trade-off” strategy. In this work, a new mechanism called neuron dissolution is introduced, by which redundant neurons produced during the computation can be removed. As applications, uniform solutions to two NP-hard problems: SAT problem and Subset Sum problem are constructed in linear time, working in a deterministic way. The neuron dissolution strategy is used to eliminate invalid solutions, and all answers to these two problems are encoded as indices of output neurons. Our results improve the one obtained in Science China Information Sciences, 2011, 1596-1607 by Pan et al. PMID:27627104

  1. Biological Impact of Bioactive Glasses and Their Dissolution Products.

    PubMed

    Hoppe, Alexander; Boccaccini, Aldo R

    2015-01-01

    For many years, bioactive glasses (BGs) have been widely considered for bone tissue engineering applications due to their ability to bond to hard as well as soft tissue (a property termed bioactivity) and for their stimulating effects on bone formation. Ionic dissolution products released during the degradation of the BG matrix induce osteogenic gene expression leading to enhanced bone regeneration. Recently, adding bioactive metallic ions (e.g. boron, copper, cobalt, silver, zinc and strontium) to silicate (or phosphate and borate) glasses has emerged as a promising route for developing novel BG formulations with specific therapeutic functionalities, including antibacterial, angiogenic and osteogenic properties. The degradation behaviour of BGs can be tailored by adjusting the glass chemistry making these glass matrices potential carrier systems for controlled therapeutic ion release. This book chapter summarises the fundamental aspects of the effect of ionic dissolution products from BGs on osteogenesis and angiogenesis, whilst discussing novel BG compositions with controlled therapeutic ion release.

  2. Economic incentives for additional critical experimentation applicable to fuel dissolution

    SciTech Connect

    Mincey, J.F.; Primm, R.T. III; Waltz, W.R.

    1981-01-01

    Fuel dissolution operations involving soluble absorbers for criticality control are among the most difficult to establish economical subcritical limits. The paucity of applicable experimental data can significantly hinder a precise determination of a bias in the method chosen for calculation of the required soluble absorber concentration. Resorting to overly conservative bias estimates can result in excessive concentrations of soluble absorbers. Such conservatism can be costly, especially if soluble absorbers are used in a throw-away fashion. An economic scoping study is presented which demonstrates that additional critical experimentation will likely lead to reductions in the soluble absorber (i.e., gadolinium) purchase costs for dissolution operations. The results indicate that anticipated savings maybe more than enough to pay for the experimental costs.

  3. Spiking Neural P Systems with Neuron Division and Dissolution.

    PubMed

    Zhao, Yuzhen; Liu, Xiyu; Wang, Wenping

    2016-01-01

    Spiking neural P systems are a new candidate in spiking neural network models. By using neuron division and budding, such systems can generate/produce exponential working space in linear computational steps, thus provide a way to solve computational hard problems in feasible (linear or polynomial) time with a "time-space trade-off" strategy. In this work, a new mechanism called neuron dissolution is introduced, by which redundant neurons produced during the computation can be removed. As applications, uniform solutions to two NP-hard problems: SAT problem and Subset Sum problem are constructed in linear time, working in a deterministic way. The neuron dissolution strategy is used to eliminate invalid solutions, and all answers to these two problems are encoded as indices of output neurons. Our results improve the one obtained in Science China Information Sciences, 2011, 1596-1607 by Pan et al. PMID:27627104

  4. Dissolution of a surfactant-containing active porous material.

    PubMed

    Brielles, Nelly; Chantraine, Florence; Viana, Marylène; Chulia, Dominique; Branlard, Paul; Rubinstenn, Gilles; Lequeux, François; Mondain-Monval, Olivier

    2008-12-15

    We have studied the imbibition and dissolution of a porous material in two separate scenarios: (1) when the porous material contains a surfactant powder and (2) when the porous material is dissolved in a surfactant solution. We show that the dissolution kinetics in both scenarios is significantly affected by the presence of the surfactant and results in an increase in the characteristic imbibition time of the porous material, which can be well understood in the framework of the classical law of capillarity. Slowing of the imbibition kinetics was found to be affected by a modification of the liquid wetting properties, but is also affected by a variation in the solubility of the porous material in the presence of the surfactant. Furthermore, there is a depletion effect of the surfactant inside the rising liquid, which is in good agreement with previous work and theoretical predictions.

  5. Studies of thermal dissolution of RDX in TNT melt

    NASA Astrophysics Data System (ADS)

    Suvorova, Natalya; Hamilton, Virginia; Oschwald, David; Smilowitz, Laura; Henson, Bryan

    2015-06-01

    The thermal response of energetic materials is studied due to its importance in issues of material safety and surety. Secondary high explosives which melt before they thermally decompose present challenging systems to model due to the addition of material flow. Composition B is a particularly challenging system due to its multiphase nature with a low melt component (TNT) and a high melt component (RDX). The dissolution of RDX crystals in molten TNT at the temperature below RDX melting point has been investigated using hot stage microscopy and Raman spectroscopy. In this paper, we will present data on the dissolution rate of RDX crystals in molten TNT as a function of temperature above the TNT melt.

  6. Bubble dissolution physics and the treatment of decompression sickness

    SciTech Connect

    Kunkle, T.D.; Beckman, E.L.

    1983-03-01

    The treatment of decompression sickness often involves both recompressing the victim and administering hyperbaric oxygen in the hope of more rapidly dissolving the bubbles which cause this malady. Although many hundreds of such treatments are conducted each year in the United States alone, the underlying physical principles governing the dissolution of such bubbles are not well understood and only empirically tested. In this paper, we present a mathematical theory of bubble dissolution that is verified by comparison with laboratory experiments. This theory suggests that the commonly employed treatment techniques would be only marginally effective, and that in many situations the bubbles that cause the disease cannot be adequately dissolved using existing techniques and facilities.

  7. Pretreatment of rice hulls by ionic liquid dissolution.

    PubMed

    Lynam, Joan G; Reza, M Toufiq; Vasquez, Victor R; Coronella, Charles J

    2012-06-01

    As a highly available waste product, rice hulls could be a starting block in replacing liquid fossil fuels. However, their silica covering can make further use difficult. This preliminary study investigates effects of dissolving rice hulls in the ionic liquids 1-ethyl-3-methylimidazolium acetate (EMIM Ac), 1-hexyl-3-methylimidazolium chloride, (HMIM Cl), and 1-allyl-3-methylimidazolium chloride (AMIM Cl), and what lignocellulosic components can be precipitated from the used ionic liquid with water and ethanol. EMIM Ac dissolution at 110 °C for 8 h was found to completely remove lignin from rice hulls, while ethanol was capable of precipitating lignin out of the used EMIM Ac. With 8h dissolution at 110 °C using HMIM Cl, approximately 20% of the cellulose in the rice hull sample can be precipitated out using water as co-solvent, while more than 60% of the hemicellulose can be precipitated with ethanol.

  8. Multivalent integrin-specific ligands enhance tissue healing and biomaterial integration.

    PubMed

    Petrie, Timothy A; Raynor, Jenny E; Dumbauld, David W; Lee, Ted T; Jagtap, Subodh; Templeman, Kellie L; Collard, David M; García, Andrés J

    2010-08-18

    Engineered biointerfaces covered with biomimetic motifs, including short bioadhesive ligands, are a promising material-based strategy for tissue repair in regenerative medicine. Potentially useful coating molecules are ligands for the integrins, major extracellular matrix receptors that require both ligand binding and nanoscale clustering for maximal signaling efficiency. We prepared coatings consisting of well-defined multimer constructs with a precise number of recombinant fragments of fibronectin (monomer, dimer, tetramer, and pentamer) to assess how nanoscale ligand clustering affects integrin binding, stem cell responses, tissue healing, and biomaterial integration. Clinical-grade titanium was grafted with polymer brushes that presented monomers, dimers, trimers, or pentamers of the alpha(5)beta(1) integrin-specific fibronectin III (7 to 10) domain (FNIII(7-10)). Coatings consisting of trimers and pentamers enhanced integrin-mediated adhesion in vitro, osteogenic signaling, and differentiation in human mesenchymal stem cells more than did surfaces presenting monomers and dimers. Furthermore, ligand clustering promoted bone formation and functional integration of the implant into bone in rat tibiae. This study establishes that a material-based strategy in which implants are coated with clustered bioadhesive ligands can promote robust implant-tissue integration. PMID:20720217

  9. Unravelling the relationship between degree of disorder and the dissolution behavior of milled glibenclamide.

    PubMed

    Mah, Pei T; Laaksonen, Timo; Rades, Thomas; Aaltonen, Jaakko; Peltonen, Leena; Strachan, Clare J

    2014-01-01

    Milling is an attractive method to prepare amorphous formulations as it does not require the use of solvents and is suitable for thermolabile drugs. One of the key critical quality attributes of milled amorphous formulations is their dissolution behavior. However, there are limited studies that have investigated the relationship between degree of disorder induced by milling and dissolution behavior. The main aim of this study was to identify the analytical technique used to characterize degree of disorder that correlates best with the recrystallization behavior during dissolution of milled glibenclamide samples. Solid state and surface changes during dissolution of milled glibenclamide samples were monitored in order to elucidate the processes that influence the dissolution behavior of milled glibenclamide samples. Glibenclamide was ball milled for different durations and analyzed using X-ray powder diffractometry (XRPD), Raman spectroscopy and differential scanning calorimetry (DSC). Recrystallization during dissolution of the milled amorphous materials was investigated using an in situ Raman setup. SEM was used to monitor the surfaces of the compacts during dissolution. XRPD, Raman spectroscopy and DSC indicated that glibenclamide was fully amorphous after milling for 30, 60, and 120 min, respectively. 'DSC amorphous' (i.e. fully amorphous according to the onset of crystallization obtained from DSC) glibenclamide samples experienced negligible recrystallization which had no effect on the dissolution profiles. Samples that were not 'DSC amorphous' experienced recrystallization which resulted in a decrease in dissolution rate. Unexpected elevated dissolution rate was observed initially during dissolution for samples milled for 15 to 45 min, and this was related to particle loss from surfaces of the disks during dissolution. In conclusion, the onset of crystallization obtained from DSC best predicts the recrystallization of glibenclamide during dissolution

  10. Dissolution of metal tritides in a simulated lung fluid

    SciTech Connect

    Cheng, Yung-Sung; Dahl, A.R.; Jow, Hong Nian

    1997-10-01

    Metal tritides including titanium tritide (Ti {sup 3}H{sub x}) and erbium tritide (Er {sup 3}H{sub x}) have been used as components of neutron generators. The current understanding of metal tritides and their radiation dosimetry for internal exposure is very limited, and the ICRP Publication 30 does not provide for tritium dosimetry in metal tritide form. However, a few papers in the literature suggest that the solubility of metal tritides could be low. The current radiation protection guidelines for metal tritide particles are based on the assumption that their biological behavior is similar to tritiated water, which could be easily absorbed into body fluid. Therefore, these particles could have relatively short biological half-lives (10 d). If the solubility is low, the biological half-life of metal tritide particles and the dosimetry of an inhalation exposure to these particles could be quite different from tritiated water. This paper describes experiments on the dissolution rate of titanium tritide particles in a simulated lung fluid. Titanium tritide particles with mean sizes of 103 {mu}m (coarse) and 0.95 {mu}m (fine) were used. The results showed that the coarse particles dissolved much more slowly than the fine particles. The long-term dissolution half times were 361 and 33 d for the coarse and fine particles, respectively. Dissolution data of the fine particles were consistent with the diffusion theory. The dissolution half times were longer than the 10-d biological half time for tritiated water in the body. This finding has significant implications for the current health protection guidelines, including annual limits of intakes and derived air concentrations.

  11. Dissolution of metal tritides in a simulated lung fluid.

    PubMed

    Cheng, Y S; Dahl, A R; Jow, H N

    1997-10-01

    Metal tritides including titanium tritide (Ti 3Hx) and erbium tritide (Er 3Hx) have been used as components of neutron generators. The current understanding of metal tritides and their radiation dosimetry for internal exposure is very limited, and the ICRP Publication 30 does not provide for tritium dosimetry in metal tritide form. However, a few papers in the literature suggest that the solubility of metal tritides could be low. The current radiation protection guidelines for metal tritide particles are based on the assumption that their biological behavior is similar to tritiated water, which could be easily absorbed into body fluid. Therefore, these particles could have relatively short biological half-lives (10 d). If the solubility is low, the biological half-life of metal tritide particles and the dosimetry of an inhalation exposure to these particles could be quite different from tritiated water. This paper describes experiments on the dissolution rate of titanium tritide particles in a simulated lung fluid. Titanium tritide particles with mean sizes of 103 microm (coarse) and 0.95 microm (fine) were used. The results showed that the coarse particles dissolved much more slowly than the fine particles. The long-term dissolution half times were 361 and 33 d for the coarse and fine particles, respectively. Dissolution data of the fine particles were consistent with the diffusion theory. The dissolution half times were longer than the 10-d biological half time for tritiated water in the body. This finding has significant implications for the current health protection guidelines, including annual limits of intakes and derived air concentrations. PMID:9314223

  12. Anaerobic microbial dissolution of transition and heavy metal oxides

    SciTech Connect

    Francis, A.J.; Dodge, C.J.

    1988-04-01

    An anaerobic N-fixing Clostridium sp. with an acetic, butyric, and lactic acid fermentation pattern, isolated from coal-cleaning waste, solubilized Fe/sub 2/O/sub 3/ and MnO/sub 2/ by direct enzymatic reduction; CdO, CuO, PbO, and ZnO were solubilized by indirect action due to the production of metabolites and the lowering of the pH of the growth medium. Extracellular heat-labile components of the cell-free spent medium obtained from cultures without oxide solubilized a significant amount of Fe/sub 2/O/sub 3/; however, direct contact with the bacterial cells resulted in the complete dissolution of the oxide. Under identical conditions, the cell-free spent medium solubilized only a small amount of MnO/sub 2/, whereas 2.3 ..mu..mol of the oxide was solubilized by direct bacterial contact. Reduction of Fe/sub 2/O/sub 3/ and MnO/sub 2/ by Clostridium sp. proceeds at different rates and, possibly, by different enzymatic systems. Fe(III) and Mn(IV) oxides appear to be used as sinks for excess electrons generated from glucose fermentation. Dialysis bag experiments with Co/sub 2/O/sub 3/ indicate that there is a slight dissolution of Co followed by precipitation or biosorption. Although Mn/sub 2/O/sub 3/, Ni/sub 2/O/sub 3/, and PbO/sub 2/ may undergo reductive dissolution from a higher to a lower oxidation state, dissolution by direct or indirect action was not observed. Also, Cr/sub 2/O/sub 3/ and NiO were not solubilized by direct or indirect action. Significant amounts of solubilized Cd, Cu, and Pb were immobilized by the bacterial biomass, and the addition of Cu/sup 2 +/ inhibited the growth of the bacterium.

  13. Surface engineering of bismuth nanocrystals to counter dissolution

    NASA Astrophysics Data System (ADS)

    Chakravarty, Shatadru; Unold, Jason; Shuboni-Mulligan, Dorela D.; Blanco-Fernandez, Barbara; Shapiro, Erik M.

    2016-07-01

    Rapid dissolution of Bi Nanocrystals (NCs) in lysosomal conditions results in poor biocompatibility. We report that an in situ surface coating of Bi nanocrystals with Ganex® V216, a cosmetic dispersant, limits its dissolution under physiological conditions. These Bi Ganex (BiG) NCs are readily encapsulated in FDA approved polymer poly(dl-lactic-co-glycolic acid) (PLGA) by an oil-in-water emulsion technique and also undergo facile SiO2 coating. BiG NCs in BiG@PLGA and BiG@SiO2 nanoparticles dissolve slowly under physiological conditions and exhibit excellent biocompatibility, as opposed to uncoated Bi NCs. Finally, these Bi nanoconstructs are shown to be strong CT CAs, even at relatively low Bi concentrations.Rapid dissolution of Bi Nanocrystals (NCs) in lysosomal conditions results in poor biocompatibility. We report that an in situ surface coating of Bi nanocrystals with Ganex® V216, a cosmetic dispersant, limits its dissolution under physiological conditions. These Bi Ganex (BiG) NCs are readily encapsulated in FDA approved polymer poly(dl-lactic-co-glycolic acid) (PLGA) by an oil-in-water emulsion technique and also undergo facile SiO2 coating. BiG NCs in BiG@PLGA and BiG@SiO2 nanoparticles dissolve slowly under physiological conditions and exhibit excellent biocompatibility, as opposed to uncoated Bi NCs. Finally, these Bi nanoconstructs are shown to be strong CT CAs, even at relatively low Bi concentrations. Electronic supplementary information (ESI) available: Detailed procedures, characterization, cellular, μCT data and ESI figures. See DOI: 10.1039/c6nr02171a

  14. IMPACT OF NUCLEAR MATERIAL DISSOLUTION ON VESSEL CORROSION

    SciTech Connect

    Mickalonis, J.; Dunn, K.; Clifton, B.

    2012-10-01

    Different nuclear materials require different processing conditions. In order to maximize the dissolver vessel lifetime, corrosion testing was conducted for a range of chemistries and temperature used in fuel dissolution. Compositional ranges of elements regularly in the dissolver were evaluated for corrosion of 304L, the material of construction. Corrosion rates of AISI Type 304 stainless steel coupons, both welded and non-welded coupons, were calculated from measured weight losses and post-test concentrations of soluble Fe, Cr and Ni.

  15. Mixing-induced dissolution in fingering reactive flow

    NASA Astrophysics Data System (ADS)

    Hidalgo, Juan J.; Cabeza, Yoar; Dentz, Marco; Carrera, Jesús

    2014-05-01

    The evolution of porosity in carbonate reservoirs during CO2 injection, and the wormhole formation in karst aquifers can be attributed to fast equilibrium reactions, which are characterized by large Damköhler numbers. Under these conditions the reaction rate is mixing-controlled, and can be quantified in terms of the mixing rate of the conservative components of the chemical system [De Simoni et al. (2005), Water. Resour. Res.]. Here, we study the calcite dissolution during the convective-driven mixing of CO2 in a carbonate saline aquifer. The CO2-brine mixture is denser than the two initial fluids, leading to a Rayleigh-Bénard-type instability known as convective mixing, which greatly accelerates CO2 dissolution. The dissolution front can display a stable or fingering shape depending on the relation of the governing forces. We explore the feedback between fluid instabilites, porosity evolution, and permeability changes by means of numerical simulations of a CO2 stationary layer dissolving into brine using an analogue-fluid system with a non-monotonic density-concentration curve [Neufeld et al. (2010), Geophys. Res. Lett.; Backhaus, et al. (2011), Phys. Rev. Lett.; Hidalgo et al. (2013), Adv. Water Resour.]. We derive an analytical expresion for the speciation contribution to the reaction rate which is valid under a wide range of reservoir conditions (pH< 8.3). This allows us to analyze systematically the impact of conservative mixing mechanisms on the dynamics of the complex reactive flow system. Our findings show how the developed porosity patterns depend on the fingering instabilities caused by the convective-driven dissolution of the CO2, the movement of the receding CO2-brine interface, and the properties of the chemical system.

  16. Salt passivation during anodic iridium dissolution in chloride melts

    SciTech Connect

    Saltykova, N.A.; Pechorskaya, L.S.; Baraboshkin, A.N.; Kotovskii, S.N.; Kosikhin, L.T.

    1986-11-01

    Anodic iridium dissolution in chloride melts at 500-700/sup 0/C was studied by potentiostatic, potentiodynamic, and galvanostatic techniques. It was found that an iridium anode is passivated by hexachloroiridates, first by the iridium (III) salt and at more positive potentials by the iridium (IV) salt. Values for anode resistance during passivation by salt films were calculated. It was shown that the morphology of the dissolving anode surface is determined by the value of polarization.

  17. Dissolution of Neptunium Oxide in Unirradiated Mark 53 Targets

    SciTech Connect

    Rudisill, T.S.

    2002-06-07

    Nine unirradiated Mark 53 targets currently stored at the K-Reactor must be dissolved to allow recovery of the neptunium content. The Mark 53 targets are an aluminum clad neptunium oxide (NpO2)/aluminum metal cermet used for the production of plutonium-238. The targets will be dissolved in H-Canyon and blended with solutions generated from routine fuel dissolutions for purification by solvent extraction

  18. On the Dissolution Behavior of Sulfur in Ternary Silicate Slags

    NASA Astrophysics Data System (ADS)

    Kang, Youn-Bae; Park, Joo Hyun

    2011-12-01

    Sulfur dissolution behavior, in terms of sulfide capacity ( C S), in ternary silicate slags (molten oxide slags composed of MO - NO - SiO2, where M and N are Ca, Mn, Fe, and Mg), is discussed based on available experimental data. Composition dependence of the sulfur dissolution, at least in the dilute region of sulfur, may be explained by taking into account the cation-anion first-nearest-neighbor (FNN) interaction (stability of sulfide) and the cation-cation second-nearest-neighbor (SNN) interaction over O anion (oxygen proportions in silicate slags). When the Gibbs energy of a reciprocal reaction MO + NS = MS + NO is positive, the sulfide capacity of slags with virtually no SiO2 or low SiO2 concentration decreases as the concentration of MO increases. However, in some slags, as SiO2 concentration increases, replacing NO by MO at a constant SiO2 concentration may increase sulfide capacity when the basicity of NO is less than that of MO. This phenomenon is observed as rotation of iso- C S lines in ternary silicate slags, and it is explained by simultaneous consideration of the stability of sulfide and oxygen proportions in the silicate slags. It is suggested that a solution model for the prediction of sulfide capacity should be based on the actual dissolution mechanism of sulfur rather than on the simple empirical correlation.

  19. Dissolution enhancement of curcumin via curcumin-prebiotic inulin nanoparticles.

    PubMed

    Fares, Mohammad M; Salem, Mu'taz Sheikh

    2015-01-01

    Dissolution enhancement of curcumin via prebiotic inulin designed to orally deliver poorly water-soluble curcumin at duodenum low acidity (pH 5.5) was investigated. Different prebiotic inulin-curcumin nanoparticles were synthesized in ethanol-water binary system at different pre-adjusted pH values. Characterization via FTIR, XRD and TGA revealed the formation of curcumin-inulin conjugates, whereas surface morphology via SEM and TEM techniques implied the formation of nanoparticle beads and nanoclusters. Prebiotic inulin-curcumin nanoparticles prepared at pH 7.0 demonstrated a maximum curcumin dissolution enhancement of ≈90% with respect to 30% for curcumin alone at pH 5.5. Power law constant values were in accordance with dissolution enhancement investigations. All samples show Fickian diffusion mechanism. XRD investigations confirm that inulin maintain its crystalline structure in curcumin-inulin conjugate structure, which confirms that it can exert successfully its prebiotic role in the gastrointestinal (GI) tract. Therefore, the use of curcumin-inulin nanoparticles can perform dual-mission in the GI tract at the duodenum environment; release of 90% of curcumin followed by prebiotic activity of inulin, which will probably play a significant role in cancer therapeutics for the coming generations.

  20. Subsurface dissolution of evaporites: where do we stand?

    NASA Astrophysics Data System (ADS)

    Zechner, Eric; Huggenberger, Peter; Konz, Markus; Zidane, Ali; Gechter, Daniel

    2010-05-01

    Evaporites of gypsum or rock salt are the most soluble common rock formation. Undersaturated groundwater in contact with evaporitic rock formations leads to subsurface dissolution, or subrosion of evaporites and, hence, to the development of karst. Depending on the geological setting, the subrosion may cause widespread land subsidence. Even small subsidence rates can significantly affect sensitive urban infrastructure, such as larger buildings, dams, power plants, or traffic lines. The factors controlling formation and shape of deep-seated subrosion are still not fully understood. The key to understand the process is related to the role of groundwater undersaturated with NaCl or CaSO4, and its driving energy. The energy can be provided by a hydrostatic head, or a density gradient, which causes groundwater to flow through the system. To further understand the process of subrosion we performed (1) laboratory dissolution experiments to study the effect induced by freshwater contacting salt; and (2) a combination of flow tank and modeling experiments to study the effect of density-driven flow in heterogeneous media. The presented results show that the development of evaporitic karst is tightly related to geologic structures. For example, the locations of normal faults control the shape of subhorizontal interstratal solution cavities. In addition, an increase of formational dip of the salt layer by a few degrees may lead to an increase of the salt dissolution rate of up to several magnitudes. The findings are used to provide more accurate predictions on risk areas for land subsidence.

  1. Dissolution-Driven Permeability Reduction of a Fractured Carbonate Caprock.

    PubMed

    Ellis, Brian R; Fitts, Jeffrey P; Bromhal, Grant S; McIntyre, Dustin L; Tappero, Ryan; Peters, Catherine A

    2013-04-01

    Geochemical reactions may alter the permeability of leakage pathways in caprocks, which serve a critical role in confining CO2 in geologic carbon sequestration. A caprock specimen from a carbonate formation in the Michigan sedimentary Basin was fractured and studied in a high-pressure core flow experiment. Inflowing brine was saturated with CO2 at 40°C and 10 MPa, resulting in an initial pH of 4.6, and had a calcite saturation index of -0.8. Fracture permeability decreased during the experiment, but subsequent analyses did not reveal calcite precipitation. Instead, experimental observations indicate that calcite dissolution along the fracture pathway led to mobilization of less soluble mineral particles that clogged the flow path. Analyses of core sections via electron microscopy, synchrotron-based X-ray diffraction imaging, and the first application of microbeam Ca K-edge X-ray absorption near edge structure, provided evidence that these occlusions were fragments from the host rock rather than secondary precipitates. X-ray computed tomography showed a significant loss of rock mass within preferential flow paths, suggesting that dissolution also removed critical asperities and caused mechanical closure of the fracture. The decrease in fracture permeability despite a net removal of material along the fracture pathway demonstrates a nonintuitive, inverse relationship between dissolution and permeability evolution in a fractured carbonate caprock. PMID:23633894

  2. Ion-specific effects influencing the dissolution of tricalcium silicate

    SciTech Connect

    Nicoleau, L.; Schreiner, E.; Nonat, A.

    2014-05-01

    It has been recently demonstrated that the dissolution kinetics of tricalcium silicate (C{sub 3}S) is driven by the deviation from its solubility equilibrium. In this article, special attention is paid to ions relevant in cement chemistry likely to interact with C{sub 3}S. In order to determine whether specific effects occur at the interface C{sub 3}S–water, particular efforts have been made to model ion activities using Pitzer's model. It has been found that monovalent cations and monovalent anions interact very little with the surface of C{sub 3}S. On the other side, divalent anions like sulfate slow down the dissolution more strongly by modifying the surface charging of C{sub 3}S. Third, aluminate ions covalently bind to surface silicate monomers and inhibit the dissolution in mildly alkaline conditions. The formation and the breaking of these bonds depend on pH and on [Ca{sup 2+}]. Thermodynamic calculations performed using DFT combined with the COSMO-RS solvation method support the experimental findings.

  3. Dissolution-Driven Permeability Reduction of a Fractured Carbonate Caprock.

    PubMed

    Ellis, Brian R; Fitts, Jeffrey P; Bromhal, Grant S; McIntyre, Dustin L; Tappero, Ryan; Peters, Catherine A

    2013-04-01

    Geochemical reactions may alter the permeability of leakage pathways in caprocks, which serve a critical role in confining CO2 in geologic carbon sequestration. A caprock specimen from a carbonate formation in the Michigan sedimentary Basin was fractured and studied in a high-pressure core flow experiment. Inflowing brine was saturated with CO2 at 40°C and 10 MPa, resulting in an initial pH of 4.6, and had a calcite saturation index of -0.8. Fracture permeability decreased during the experiment, but subsequent analyses did not reveal calcite precipitation. Instead, experimental observations indicate that calcite dissolution along the fracture pathway led to mobilization of less soluble mineral particles that clogged the flow path. Analyses of core sections via electron microscopy, synchrotron-based X-ray diffraction imaging, and the first application of microbeam Ca K-edge X-ray absorption near edge structure, provided evidence that these occlusions were fragments from the host rock rather than secondary precipitates. X-ray computed tomography showed a significant loss of rock mass within preferential flow paths, suggesting that dissolution also removed critical asperities and caused mechanical closure of the fracture. The decrease in fracture permeability despite a net removal of material along the fracture pathway demonstrates a nonintuitive, inverse relationship between dissolution and permeability evolution in a fractured carbonate caprock.

  4. Attenuation of Glass Dissolution in the Presence of Natural Additives

    NASA Technical Reports Server (NTRS)

    Sang, Jing C.; Barkatt, Aaron; OKeefe, John A.

    1993-01-01

    The study described here explored the dissolution kinetics of glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase. The results demonstrated the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. The study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses as well as to better understanding of the environmental degradation of natural and ancient glasses.

  5. Microscopic modeling of confined crystal growth and dissolution.

    PubMed

    Høgberget, Jørgen; Røyne, Anja; Dysthe, Dag K; Jettestuen, Espen

    2016-08-01

    We extend the (1+1)-dimensional fluid solid-on-solid (SOS) model to include a confining flat surface opposite to the SOS surface subject to a constant load. This load is balanced by a repulsive surface-surface interaction given by an ansatz which agrees with known analytical solutions in the limit of two separated flat surfaces. Mechanical equilibrium is imposed at all times by repositioning the confining surface. By the use of kinetic Monte Carlo (KMC) we calculate how the equilibrium concentration (deposition rate) depends on the applied load, and find it to reproduce analytical thermodynamics independent of the parameters of the interaction ansatz. We also study the dependency between the surface roughness and the saturation level as we vary the surface tension, and expand on previous analyses of the asymmetry between growth and dissolution by parametrizing the linear growth rate constant for growth and dissolution separately. We find the presence of a confining surface to affect the speed of growth and dissolution equally. PMID:27627386

  6. Dissolution-Driven Permeability Reduction of a Fractured Carbonate Caprock

    PubMed Central

    Ellis, Brian R.; Fitts, Jeffrey P.; Bromhal, Grant S.; McIntyre, Dustin L.; Tappero, Ryan; Peters, Catherine A.

    2013-01-01

    Abstract Geochemical reactions may alter the permeability of leakage pathways in caprocks, which serve a critical role in confining CO2 in geologic carbon sequestration. A caprock specimen from a carbonate formation in the Michigan sedimentary Basin was fractured and studied in a high-pressure core flow experiment. Inflowing brine was saturated with CO2 at 40°C and 10 MPa, resulting in an initial pH of 4.6, and had a calcite saturation index of −0.8. Fracture permeability decreased during the experiment, but subsequent analyses did not reveal calcite precipitation. Instead, experimental observations indicate that calcite dissolution along the fracture pathway led to mobilization of less soluble mineral particles that clogged the flow path. Analyses of core sections via electron microscopy, synchrotron-based X-ray diffraction imaging, and the first application of microbeam Ca K-edge X-ray absorption near edge structure, provided evidence that these occlusions were fragments from the host rock rather than secondary precipitates. X-ray computed tomography showed a significant loss of rock mass within preferential flow paths, suggesting that dissolution also removed critical asperities and caused mechanical closure of the fracture. The decrease in fracture permeability despite a net removal of material along the fracture pathway demonstrates a nonintuitive, inverse relationship between dissolution and permeability evolution in a fractured carbonate caprock. PMID:23633894

  7. Cross-polarization for dissolution dynamic nuclear polarization.

    PubMed

    Batel, Michael; Däpp, Alexander; Hunkeler, Andreas; Meier, Beat H; Kozerke, Sebastian; Ernst, Matthias

    2014-10-21

    Dynamic nuclear polarization (DNP) in combination with subsequent dissolution of the sample allows the detection of low-γ nuclei in the solution state with a signal gain of up to tens of thousand times compared to experiments starting from Boltzmann conditions. The long polarization build-up times of typically more than one hour are a drawback of this technique. The combination of dissolution DNP with cross-polarization (CP) in the solid state was shown to have the potential to overcome this disadvantage. In this article we discuss the cross-polarization step under dissolution DNP conditions in more detail. We show that adiabatic half-passage pulses allow us to enhance the CP efficiency in power-limited DNP probes. As a low-power alternative to Hartmann-Hahn CP we also demonstrate the applicability of frequency-swept de- and re-magnetization pulses for polarization transfer via dipolar order. We investigate the implications and restrictions of the common solid-state DNP mechanisms to the DNP-CP technique and apply a spin-thermodynamic model based on the thermal-mixing mechanism. The model allows us to investigate the dynamics of the polarization levels in a system with two nuclear Zeeman reservoirs and explains the enhanced DNP efficiency upon solvent deuteration within a spin-thermodynamic picture. PMID:25182534

  8. Enhanced dissolution of oxcarbazepine microcrystals using a static mixer process.

    PubMed

    Douroumis, D; Fahr, A

    2007-10-01

    The purpose of this study was to form micronized powders of Oxcarbazepine (OXC), a poorly water-soluble drug, using a static mixer technique to enhance the dissolution rate. Controlled precipitation was achieved injecting the organic OXC solution rapidly into an aqueous methylcellulose (MC) protective solution by means of a static mixer thus providing turbulent and homogeneous mixing. Furthermore, a factorial design was implemented for data analysis. The physicochemical properties of the freeze-dried dispersions were evaluated by differential scanning calorimetry (DSC), infrared spectroscopy (FTIR) and X-ray diffraction (XRD). Drug microcrystals showed a narrow size distribution with approximately 2 microm mean particle size and high drug loading. DSC and FTIR studies revealed that the drug remained in crystalline state and no drug-polymer interaction occurred. The dissolution studies showed enhanced dissolution of OXC microcrystals compared to the pure drug. The static mixer technique was proved capable for micro-sized polymeric particles. This is an inexpensive, less time consuming and fully scalable process for development of poorly soluble drugs. PMID:17588726

  9. Dissolution Behavior of Plutonium Containing Zirconia-Magnesia Ceramics

    SciTech Connect

    Kiel Holliday; Thomas Hartmann; Gary Cerefice; Ken Czerwinski

    2012-03-01

    This study explores the dissolution properties of zirconia-magnesia ceramics containing plutonium as the basis of an inert atrix nuclear fuel. The magnesium oxide phase remains pure MgO, while the zirconia incorporates a small amount of magnesium oxide along with all of the plutonium oxide and erbium oxide. The performance of the material under reactor and repository environments was examined. Reactor conditions are examined using a pressure vessel to expose the material to 300 degrees C water. To assess the performance of the material as a waste form it was submerged in 90 degrees C water for 1000 h. In both aqueous dissolution studies there was minimal release of less than 0.8 wt.% of plutonium from the material. To examine the potential for recycling, the dissolution behavior of the fuel matrix was examined in acidic solutions: pure nitric acid and a nitric acid-hydrofluoric acid-peroxide solution. Both acidic media exhibit potential for dissolving plutonium from the zirconia matrix. The experiments performed in this study are meant to lay a foundation for the chemical performance of zirconia-magnesia inert matrix fuel containing fissile material and burnable poison.

  10. Can H2 enhance the oxidative dissolution of UO2?

    NASA Astrophysics Data System (ADS)

    Barreiro Fidalgo, Alexandre; Jonsson, Mats

    2016-08-01

    Understanding the mechanism and kinetics of spent nuclear fuel dissolution in water is of key-importance for the safety assessment of deep geological repositories for spent nuclear fuel [1-5]. For UO2-based fuel, radiation induced oxidative dissolution of the fuel matrix is of considerable importance as this will enhance the release of fission products and actinides by several orders of magnitude [2-4]. This process has been studied extensively over several decades and can now be considered to be fairly well understood [2-6]. The aqueous radiolysis product identified as mainly being responsible for the oxidative dissolution of UO2 is H2O2[7]. In addition to oxidation of U(IV) to U(VI), H2O2 also undergoes catalytic decomposition on the UO2-surface [8,9]. In fact, it has been shown that catalytic decomposition is the major route on UO2-pellets [10,11]. In recent years it has been shown that this process involves the formation of surface bound hydroxyl radicals [12]. The mechanism of the catalytic decomposition is depicted in reaction (1-3).

  11. Dissolution-Driven Permeability Reduction of a Fractured Carbonate Caprock

    SciTech Connect

    Ellis, Brian R.; Fitts, Jeffrey P.; Bromhal, Grant S.; McIntyre, Dustin L.; Tappero, Ryan; Peters, Catherine A.

    2013-04-01

    Geochemical reactions may alter the permeability of leakage pathways in caprocks, which serve a critical role in confining CO{sub 2} in geologic carbon sequestration. A caprock specimen from a carbonate formation in the Michigan sedimentary Basin was fractured and studied in a high-pressure core flow experiment. Inflowing brine was saturated with CO{sub 2} at 40°C and 10MPa, resulting in an initial pH of 4.6, and had a calcite saturation index of -0.8. Fracture permeability decreased during the experiment, but subsequent analyses did not reveal calcite precipitation. Instead, experimental observations indicate that calcite dissolution along the fracture pathway led to mobilization of less soluble mineral particles that clogged the flow path. Analyses of core sections via electron microscopy, synchrotron-based X-ray diffraction imaging, and the first application of microbeam Ca K-edge X-ray absorption near edge structure, provided evidence that these occlusions were fragments from the host rock rather than secondary precipitates. X-ray computed tomography showed a significant loss of rock mass within preferential flow paths, suggesting that dissolution also removed critical asperities and caused mechanical closure of the fracture. The decrease in fracture permeability despite a net removal of material along the fracture pathway demonstrates a nonintuitive, inverse relationship between dissolution and permeability evolution in a fractured carbonate caprock.

  12. Dissolution behavior of plutonium containing zirconia-magnesia ceramics

    NASA Astrophysics Data System (ADS)

    Holliday, Kiel; Hartmann, Thomas; Cerefice, Gary; Czerwinski, Ken

    2012-03-01

    This study explores the dissolution properties of zirconia-magnesia ceramics containing plutonium as the basis of an inert matrix nuclear fuel. The magnesium oxide phase remains pure MgO, while the zirconia incorporates a small amount of magnesium oxide along with all of the plutonium oxide and erbium oxide. The performance of the material under reactor and repository environments was examined. Reactor conditions are examined using a pressure vessel to expose the material to 300 °C water. To assess the performance of the material as a waste form it was submerged in 90 °C water for 1000 h. In both aqueous dissolution studies there was minimal release of less than 0.8 wt.% of plutonium from the material. To examine the potential for recycling, the dissolution behavior of the fuel matrix was examined in acidic solutions: pure nitric acid and a nitric acid-hydrofluoric acid-peroxide solution. Both acidic media exhibit potential for dissolving plutonium from the zirconia matrix. The experiments performed in this study are meant to lay a foundation for the chemical performance of zirconia-magnesia inert matrix fuel containing fissile material and burnable poison.

  13. The Effect of Radiation Damage on Zirconolite Dissolution

    SciTech Connect

    Smith, Katherine L.; Zhang, Zhaoming; McGlinn, Peter; Attard, Darren; Li, Huijing; Lumpkin, Gregory R.; Colella, Michael; McLeod, Terry; Aly, Zaynab; Loi, Elaine; Leung, Sammy; Hart, Kaye P.; Ridgway, Mark; Weber, William J.; Thevuthasan, Suntharampillai; RJ Finch and DB Bullen

    2003-08-20

    Polished tiles (7x7x2 mm3) of Nd-bearing zirconolite were fabricated and then some were irradiated on both large faces with 3 MeV or 2 MeV Au2+ ions (total fluence of {approx} 1 x 1015 ions/cm2) in order to render the zirconolite amorphous and so simulate displacement damage caused by alpha decay. Both the irradiated and non-irradiated tiles were then subjected to static dissolution tests in 0.01M nitric solution (pH2) at 90 C, for periods of 0-1, 1-7, 7-14 and 14-28 days. It was found that radiation damage did not affect the dissolution rate of zirconolite as indicated by the elemental leach rates of Nd, Ti, Ca and Al. The results of solution analyses are consistent with those obtained from X-ray Photoelectron Spectroscopy (XPS) in that the Ca, Nd, Ti and Al concentrations in the top surface layer (< 5 nm) all decreased with respect to that of Zr after dissolution testing, and the leached surface composition of the non-irradiated zirconolite is very similar to that of the two irradiated specimens. The implications of these results are discussed in the context of previous work.

  14. Microscopic modeling of confined crystal growth and dissolution

    NASA Astrophysics Data System (ADS)

    Høgberget, Jørgen; Røyne, Anja; Dysthe, Dag K.; Jettestuen, Espen

    2016-08-01

    We extend the (1+1)-dimensional fluid solid-on-solid (SOS) model to include a confining flat surface opposite to the SOS surface subject to a constant load. This load is balanced by a repulsive surface-surface interaction given by an ansatz which agrees with known analytical solutions in the limit of two separated flat surfaces. Mechanical equilibrium is imposed at all times by repositioning the confining surface. By the use of kinetic Monte Carlo (KMC) we calculate how the equilibrium concentration (deposition rate) depends on the applied load, and find it to reproduce analytical thermodynamics independent of the parameters of the interaction ansatz. We also study the dependency between the surface roughness and the saturation level as we vary the surface tension, and expand on previous analyses of the asymmetry between growth and dissolution by parametrizing the linear growth rate constant for growth and dissolution separately. We find the presence of a confining surface to affect the speed of growth and dissolution equally.

  15. Comparison between donor substrates for biologically enhanced tetrachloroethene DNAPL dissolution.

    PubMed

    Yang, Yanru; McCarty, Perry L

    2002-08-01

    Tetrachloroethene (PCE) dense nonaqueous-phase liquid (DNAPL) can act as a persistent groundwater contamination source for decades. Biologically enhanced dissolution of pure PCE DNAPL has potential for reducing DNAPL longevity as indicated previously (Environ. Sci. Technol. 2000, 34, 2979). Reported here are expanded studies to evaluate donor substrates that offer different remediation strategies for bioenhanced DNAPL dissolution, including pentanol (soluble substrate, fed continuously), calcium oleate (insoluble substrate, placed in column initially by alternate pumping of sodium oleate and calcium chloride), and olive oil (mixed with PCE and placed in column initially). Compared with a no-substrate column control, the DNAPL dissolution rate was enhanced about three times when directly coupled with biological transformation. The major degradation product formed was cDCE, but significant amounts of VC and ethene were also found with some columns. Extensive methanogenesis, which reduced PCE transformation, occurred in both the pentanol-fed and oleate-amended columns, but not in the olive-oil-amended column, suggesting that methanogens managed to colonize column niches where PCE DNAPL was not present. Detrimental methane production in the pentanol-fed column was nearly eliminated by presaturating the feed solution with PCE. These results suggest potential DNAPL remediation strategies to enhance dehalogenation while controlling competitive methanogenic utilization of donor substrates.

  16. The BRAG and GM2003 Models for Glass Dissolution

    SciTech Connect

    Aertsens, Marc

    2007-07-01

    The GM2003 model extends the r(t) glass dissolution model with water diffusion through the diffusion layer. Boron and alkali diffusion through the diffusion layer is described by introducing a retention factor K{sub d,i} between boron/alkali and water in the diffusion layer. Introducing a boron/alkali diffusion coefficient, the BRAG model describes boron/alkali diffusion in the diffusion layer as well. It is shown that both models are consistent with each other and an expression is derived for the boron/alkali diffusion coefficient (BRAG) as a function of both parameters of GM2003: the retention factor K{sub d,i} and the water diffusion coefficient D{sub H{sub 2}}{sub O} in the diffusion layer. From dissolution data only, it is possible to fit the value for the boron/alkali diffusion coefficient in the diffusion layer but due to correlations the individual values of both parameters K{sub d,i} and DH{sub 2}O of GM2003 cannot be determined. From theoretical considerations follows that the K{sub d,i} value for boron/alkali should be slightly larger than 0.1 kg/liter. A user friendly code for the BRAG model allows automatic fits of glass dissolution data in water. (authors)

  17. Progress in alkaline peroxide dissolution of low-enriched uranium metal and silicide targets

    SciTech Connect

    Chen, L.; Dong, D.; Buchholz, B.A.; Vandegrift, G.F.; Wu, D.

    1996-12-31

    This paper reports recent progress on two alkaline peroxide dissolution processes: the dissolution of low-enriched uranium metal and silicide (U{sub 3}Si{sub 2}) targets. These processes are being developed to substitute low-enriched for high-enriched uranium in targets used for production of fission-product {sup 99}Mo. Issues that are addressed include (1) dissolution kinetics of silicide targets, (2) {sup 99}Mo lost during aluminum dissolution, (3) modeling of hydrogen peroxide consumption, (4) optimization of the uranium foil dissolution process, and (5) selection of uranium foil barrier materials. Future work associated with these two processes is also briefly discussed.

  18. Automatic generation of bioinformatics tools for predicting protein–ligand binding sites

    PubMed Central

    Banno, Masaki; Ueki, Kokoro; Saad, Gul; Shimizu, Kentaro

    2016-01-01

    Motivation: Predictive tools that model protein–ligand binding on demand are needed to promote ligand research in an innovative drug-design environment. However, it takes considerable time and effort to develop predictive tools that can be applied to individual ligands. An automated production pipeline that can rapidly and efficiently develop user-friendly protein–ligand binding predictive tools would be useful. Results: We developed a system for automatically generating protein–ligand binding predictions. Implementation of this system in a pipeline of Semantic Web technique-based web tools will allow users to specify a ligand and receive the tool within 0.5–1 day. We demonstrated high prediction accuracy for three machine learning algorithms and eight ligands. Availability and implementation: The source code and web application are freely available for download at http://utprot.net. They are implemented in Python and supported on Linux. Contact: shimizu@bi.a.u-tokyo.ac.jp Supplementary information: Supplementary data are available at Bioinformatics online. PMID:26545824

  19. Revealing a steroid receptor ligand as a unique PPAR[gamma] agonist

    SciTech Connect

    Lin, Shengchen; Han, Ying; Shi, Yuzhe; Rong, Hui; Zheng, Songyang; Jin, Shikan; Lin, Shu-Yong; Lin, Sheng-Cai; Li, Yong

    2012-06-28

    Peroxisome proliferator-activated receptor gamma (PPAR{gamma}) regulates metabolic homeostasis and is a molecular target for anti-diabetic drugs. We report here the identification of a steroid receptor ligand, RU-486, as an unexpected PPAR{gamma} agonist, thereby uncovering a novel signaling route for this steroid drug. Similar to rosiglitazone, RU-486 modulates the expression of key PPAR{gamma} target genes and promotes adipocyte differentiation, but with a lower adipogenic activity. Structural and functional studies of receptor-ligand interactions reveal the molecular basis for a unique binding mode for RU-486 in the PPAR{gamma} ligand-binding pocket with distinctive properties and epitopes, providing the molecular mechanisms for the discrimination of RU-486 from thiazolidinediones (TZDs) drugs. Our findings together indicate that steroid compounds may represent an alternative approach for designing non-TZD PPAR{gamma} ligands in the treatment of insulin resistance.

  20. Colloidal metal oxide nanocrystal catalysis by sustained chemically driven ligand displacement

    NASA Astrophysics Data System (ADS)

    de Roo, Jonathan; van Driessche, Isabel; Martins, José C.; Hens, Zeger

    2016-05-01

    Surface chemistry is a key enabler for colloidal nanocrystal applications. In this respect, metal oxide nanocrystals (NCs) stand out from other NCs as carboxylic acid ligands adsorb on their surface by dissociation to carboxylates and protons, the latter proving essential in electron transfer reactions. Here, we show that this binding motif sets the stage for chemically driven ligand displacement where the binding of amines or alcohols to HfO2 NCs is promoted by the conversion of a bound carboxylic acid into a non-coordinating amide or ester. Furthermore, the sustained ligand displacement, following the addition of excess carboxylic acid, provides a catalytic pathway for ester formation, whereas the addition of esters leads to NC-catalysed transesterification. Because sustained, chemically driven ligand displacement leaves the NCs--including their surface composition--unchanged and preserves colloidal stability, metal oxide nanocrystals are thus turned into effective nanocatalysts that bypass the tradeoff between colloidal stability and catalytic activity.