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Sample records for hydroxide anion interfacial

  1. Investigating hydroxide anion interfacial activity by classical and multi-state empirical valence bond molecular dynamics simulations

    SciTech Connect

    Dang, Liem X.; Wick, Collin D.

    2009-06-04

    Molecular dynamics simulations were carried out to understand the propensity of the hydroxide anion for the air-water interface. Two classes of molecular models were used, a classical polarizable model, and a polarizable multi-state empirical valence bond (MS-EVB) potential. The latter model was parameterized to reproduce the structures of small hydroxide-water clusters based on proton reaction coordinates. Furthermore, nuclear quantum effects were introduced into the MS-EVB model implicitly by refitting its potential energy function to account for them. The final MS-EVB model showed reasonable agreement with experiment and ab initio molecular dynamics simulations for dynamical and structural properties. The free energy profiles for both the classical and MS-EVB models were mapped out across the air-water interface, and the classical model gave a higher free energy at the interface with respect to bulk. The MS-EVB model gave a hydroxide anion that approached very close to the interface before it had a sharp increase in free energy at the Gibbs dividing surface. This showed a hydroxide anion that was present at the interface, but strongly repelled from its outer edge near the air. This work was supported by the US Department of Energy's Office of Basec Energy Sciences, Chemical Sciences program. Pacific northwest national Laboratory is operated by Battelle for DOE.

  2. Synthesis and Characterization of Imidazolium Linear Bisphenol Polycarbonate Hydroxides for Anion Exchange Membrane.

    PubMed

    Jang, Hohyoun; Hossain, Md Awlad; Lee, Soonho; Ha, Jaesung; Yoo, Jihoo; Kim, Kyungchul; Kim, Whangi

    2015-11-01

    A novel anion exchange membrane of imidazolium functionalized bisphenol polycarbonate was prepared for application in alkaline fuel cell. Di-imidazolium polycarbonate anionic membrane was synthesized by sequential interfacial polymerization, chloromethylation, substitution with 1-methylimidazole and ion exchange with 1.0 M KOH. Chloromethylation reaction was quantitative to achieve a high content of hydroxide ions. Introduction of conjugated imidazole ring in polymer plays an important role to improve both thermal and chemical stability. Bisphenol polycarbonate is a flexible polymer and shows a good solubility in polar organic solvent. The alkaline imidazolium bisphenol polycarbonate rendered an elevated molecular weight with excellent solubility in polar aprotic solvent. Different levels of substitution and ion exchange were investigated; the resulting membranes showed high ion exchange capacities (IECs) of up to 2.15 mmol g(-1). The imidazolium-functionalized copolymer membranes showed lower water affinity (14.2-42.8% at 30 degrees C) that satisfied an essential criterion for fuel cell application. The chemical structure of the imidazolium functionalized polycarbonate membrane was confirmed by 1H NMR spectroscopy, and also the membrane properties were evaluated by thermogravimetric analysis (TGA) and water uptake (WU), IEC and conductivity assessment. They exhibited hydroxide conductivity above 10(-2) S cm(-1) at room temperature and good chemical stability for up to five days without significant losses of ion conductivity.

  3. Frog striated muscle is permeable to hydroxide and buffer anions.

    PubMed

    Venosa, R A; Kotsias, B A; Horowicz, P

    1994-04-01

    Hydroxide, bicarbonate and buffer anion permeabilities in semitendinosus muscle fibers of Rana pipiens were measured. In all experiments, the fibers were initially equilibrated in isotonic, high K2SO4 solutions at pHo = 7.2 buffered with phosphate. Two different methods were used to estimate permeabilities: (i) membrane potential changes were recorded in response to changes in external ion concentrations, and (ii) intracellular pH changes were recorded in response to changes in external concentrations of ions that alter intracellular pH. Constant field equations were used to calculate relative or absolute permeabilities. In the first method, to increase the size of the membrane potential change produced by a sudden change in anion entry, external K+ was replaced by Cs+ prior to changes of the anion under study. At constant external Cs+ activity, a hyperpolarization results from increasing external pH from 7.2 to 10.0 or higher, using either CAPS (3-[cyclohexylamino]-1-propanesulfonic acid) or CHES (2-[N-cyclohexylamino]-ethanesulfonic acid) as buffer. For each buffer, the protonated form is a zwitterion of zero net charge and the nonprotonated form is an anion. Using reported values of H+ permeability, calculations show that the reduction in [H+]o cannot account for the hyperpolarizations produced by alkaline solutions. Membrane hyperpolarization increases with increasing total external buffer concentration at constant external pH, and with increasing external pH at constant external buffer anion concentration. Taken together, these observations indicate that both OH- and buffer anions permeate the surface membrane. The following relative permeabilities were obtained at pHo = 10.0 +/- 0.3: (POH/PK) = 890 +/- 150, (PCAPS/PK) = 12 +/- 2, (PCHES/PK) = 5.3 +/- 0.9, and (PNO3/PK) = 4.7 +/- 0.5. PNO3/PK was independent of pHo up to 10.75. At pHo = 9.6, (PHCO3/PK) = 0.49 +/- 0.03; at pHo = 8.9, (PCl/PK) = 18 +/- 2 and at pHo = 7.1, (PHEPES/PK) = 20 +/- 2. In the second

  4. Propensity of Hydrated Excess Protons and Hydroxide Anions for the Air-Water Interface.

    PubMed

    Tse, Ying-Lung Steve; Chen, Chen; Lindberg, Gerrick E; Kumar, Revati; Voth, Gregory A

    2015-10-01

    Significant effort has been undertaken to better understand the molecular details governing the propensity of ions for the air-water interface. Facilitated by computationally efficient reactive molecular dynamics simulations, new and statistically conclusive molecular-scale results on the affinity of the hydrated excess proton and hydroxide anion for the air-water interface are presented. These simulations capture the dynamic bond breaking and formation processes (charge defect delocalization) that are important for correctly describing the solvation and transport of these complex species. The excess proton is found to be attracted to the interface, which is correlated with a favorable enthalpic contribution and consistent with reducing the disruption in the hydrogen bond network caused by the ion complex. However, a recent refinement of the underlying reactive potential energy function for the hydrated excess proton shows the interfacial attraction to be weaker, albeit nonzero, a result that is consistent with the experimental surface tension measurements. The influence of a weak hydrogen bond donated from water to the protonated oxygen, recently found to play an important role in excess hydrated proton transport in bulk water, is seen to also be important for this study. In contrast, the hydroxide ion is found to be repelled from the air-water interface. This repulsion is characterized by a reduction of the energetically favorable ion-water interactions, which creates an enthalpic penalty as the ion approaches the interface. Finally, we find that the fluctuation in the coordination number around water sheds new light on the observed entropic trends for both ions. PMID:26366480

  5. Fluoride adsorption onto amorphous aluminum hydroxide: Roles of the surface acetate anions.

    PubMed

    Zhang, Yong-Xing; Jia, Yong

    2016-12-01

    Amorphous aluminum hydroxide with hydroxyl groups, acetate anions and chlorine anions enriched surface was synthesized, and was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption-desorption isotherms. Batch experiments were performed to study the influence of various experimental parameters such as contact time, initial fluoride concentration, temperature, pH value and the presence of competing anions on the adsorption of fluoride on amorphous aluminum hydroxide. The kinetic data was well fitted to pseudo-second-order model. The fluoride adsorption on the amorphous aluminum hydroxide can be well described by the Langmuir model, and the maximum adsorption capacity was 63.94mgg(-1) at pH 7.0. Thermodynamic parameters including the Gibbs free energy, standard enthalpy and standard entropy were calculated, and the results suggested that the adsorption of fluoride on the amorphous aluminum hydroxide was a feasible, spontaneous and exothermic process. The adsorption mechanism was revealed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis. The results suggested that the surface acetate anions and surface chlorine anions played important roles in the fluoride removal process. PMID:27565961

  6. Interfacial charging phenomena of aluminum (hydr)oxides

    SciTech Connect

    Hiemstra, T.; Yong, H.; Van Riemsdijk, W.H.

    1999-08-31

    The interfacial charging of Al(OH){sub 3} (gibbsite and bayerite) and Al{sub 2}O{sub 3} has been studied. For Al(OH){sub 3} it can be shown that the very strong variation in charging behavior for different preparations is related to the relative presence of differently reacting crystal planes. The edge faces of the hexagonal gibbsite crystals are proton reactive over the whole pH range, in contrast to the 001 plane, which is mainly uncharged below pH = 10. On this 001 face only doubly coordinated surface groups are found, in contrast to the edges which also have singly coordinated surface groups. The results are fully in agreement with the predictions of the Multi site complexation (MUSIC) model. The proton adsorption, electrolyte ion adsorption, and shift of the IEP of gibbsite and aluminum oxide have been modeled simultaneously. For gibbsite, the ion pair formation of Na is larger than that of Cl, as is evidenced by modeling the experimentally observed upward shift on the IEP and charge reversal at high electrolyte concentrations. All these experimental results can be satisfactorily modeled with the MUSIC model, including the experimental surface potential of aluminum oxide (ISFET).

  7. Strong interfacial attrition developed by oleate/layered double hydroxide nanoplatelets dispersed into poly(butylene succinate).

    PubMed

    Zhou, Qian; Verney, Vincent; Commereuc, Sophie; Chin, In-Joo; Leroux, Fabrice

    2010-09-01

    Poly(butylene succinate) (PBS) nanocomposite structure was studied as a function of the filler percentage loading. The resulting state of dispersion was evaluated by XRD and TEM, and the interfacial attrition between PBS chain and lamellar platelets by the melt rheological properties. Hybrid organic inorganic (O/I) layered double hydroxide (LDH) organo-modified by oleate anions was used as filler. It was found that the confinement supplied by the LDH framework forces the interleaved organic molecule to be more distant from each other than in the case of oleate salt, this having as an effect to decrease strongly the homonuclear intermolecular (1)H(1)H dipolar interaction. An additional consequence of this relatively free molecular rotation, affecting the (13)C CPMAS response as well, is to facilitate the delamination of the 2D-stacked layers during extrusion since an quasi-exfoliated PBS:Mg(2)Al/oleate structure is observed for filler loading lower than 5% w/w. This is in association to a non-linear viscoelasticity in the low-omega region and the observed shear-thinning tendency compares better than other PBS:silicate nanocomposite derivatives and is here explained by the presence of a percolated LDH nanoparticle network. Indeed the plastic deformation in the low-omega region is found to be restricted by well-dispersed LDH tactoids in association with a rather strong attrition phenomenon between tethered oleate anions and PBS chains.

  8. Absorption of the selenite anion from aqueous solutions by thermally activated layered double hydroxide.

    PubMed

    Liu, Rui; Frost, Ray L; Martens, Wayde N

    2009-03-01

    The presence of selenite or selenate in potable water is a health hazard especially when consumed over a long period of time. Its removal from potable water is of importance. This paper reports technology for the removal of selenite from water through the use of thermally activated layered double hydroxides. Mg/Al hydrotalcites with selenite in the interlayer were prepared at different times from 0.5 to 20 h through ion exchange. X-ray diffraction of the MgAlSeO3 hydrotalcites indicates that the selenite anion entered the interlayer spacing of Mg/Al hydrotalcite and MgAlSeO3 hydrotalcite was formed. Raman spectra proved the presence of selenite anion in the hydrotalcite interlayer as the counter anion. The band intensity and width of MgAlSeO3 hydrotalcite in the region of 3800-3000 cm(-1) increase with the adsorption of selenite by the Mg/Al hydrotalcite. The characteristic bands of free selenite anions in the MgAlSeO3 hydrotalcites are located between the region between 850 and 800 cm(-1). The Raman spectra of the lower wave number region of 550-500 cm(-1) show a shift toward higher wave numbers with adsorption of the selenite. An estimation of the amount of selenite anion removed by the thermally activated layered double hydroxide was obtained through the measurement of the intensity of the selenite Raman bands at 814 and 835 cm(-1) resulting from the amount of selenite anion remaining in solution. Thermally activated LDHs provide a mechanism for removing selenite anions from aqueous solutions.

  9. Rapid exchange between atmospheric CO2 and carbonate anion intercalated within magnesium rich layered double hydroxide.

    PubMed

    Sahoo, Pathik; Ishihara, Shinsuke; Yamada, Kazuhiko; Deguchi, Kenzo; Ohki, Shinobu; Tansho, Masataka; Shimizu, Tadashi; Eisaku, Nii; Sasai, Ryo; Labuta, Jan; Ishikawa, Daisuke; Hill, Jonathan P; Ariga, Katsuhiko; Bastakoti, Bishnu Prasad; Yamauchi, Yusuke; Iyi, Nobuo

    2014-10-22

    The carbon cycle, by which carbon atoms circulate between atmosphere, oceans, lithosphere, and the biosphere of Earth, is a current hot research topic. The carbon cycle occurring in the lithosphere (e.g., sedimentary carbonates) is based on weathering and metamorphic events so that its processes are considered to occur on the geological time scale (i.e., over millions of years). In contrast, we have recently reported that carbonate anions intercalated within a hydrotalcite (Mg0.75Al0.25(OH)2(CO3)0.125·yH2O), a class of a layered double hydroxide (LDH), are dynamically exchanging on time scale of hours with atmospheric CO2 under ambient conditions. (Ishihara et al., J. Am. Chem. Soc. 2013, 135, 18040-18043). The use of (13)C-labeling enabled monitoring by infrared spectroscopy of the dynamic exchange between the initially intercalated (13)C-labeled carbonate anions and carbonate anions derived from atmospheric CO2. In this article, we report the significant influence of Mg/Al ratio of LDH on the carbonate anion exchange dynamics. Of three LDHs of various Mg/Al ratios of 2, 3, or 4, magnesium-rich LDH (i.e., Mg/Al ratio = 4) underwent extremely rapid exchange of carbonate anions, and most of the initially intercalated carbonate anions were replaced with carbonate anions derived from atmospheric CO2 within 30 min. Detailed investigations by using infrared spectroscopy, scanning electron microscopy, powder X-ray diffraction, elemental analysis, adsorption, thermogravimetric analysis, and solid-state NMR revealed that magnesium rich LDH has chemical and structural features that promote the exchange of carbonate anions. Our results indicate that the unique interactions between LDH and CO2 can be optimized simply by varying the chemical composition of LDH, implying that LDH is a promising material for CO2 storage and/or separation.

  10. Anion-intercalated layered double hydroxides modified test strips for detection of heavy metal ions.

    PubMed

    Wang, Nan; Sun, Jianchao; Fan, Hai; Ai, Shiyun

    2016-01-01

    In this work, a novel approach for facile and rapid detection of heavy metal ions using anion-intercalated layered double hydroxides (LDHs) modified test strips is demonstrated. By intercalating Fe(CN)6(4-) or S(2-) anions into the interlayers of LDHs on the filter paper, various heavy metal ions can be easily detected based on the color change before and after reaction between the anions and the heavy metal ions. Upon the dropping of heavy metal ions solutions to the test strips, the colors of the test strips changed instantly, which can be easily observed by naked eyes. With the decrease of the concentration, the color depth changed obviously. The lowest detection concentration can be up to 1×10(-6) mol L(-1). Due to the easily intercalation of anions into the interlayer of the LDHs on test trips, this procedure provides a general method for the construction of LDHs modified test strips for detection of heavy metal ions. The stability of the prepared test strips is investigated. Furthermore, all the results were highly reproducible. The test strips may have potential applications in environmental monitoring fields.

  11. Energy and structure of bonds in the interaction of organic anions with layered double hydroxide nanosheets: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Tsukanov, A. A.; Psakhie, S. G.

    2016-01-01

    The application of hybrid and hierarchical nanomaterials based on layered hydroxides and oxyhydroxides of metals is a swiftly progressing field in biomedicine. Layered double hydroxides (LDH) possess a large specific surface area, significant surface electric charge and biocompatibility. Their physical and structural properties enable them to adsorb various kinds of anionic species and to transport them into cells. However, possible side effects resulting from the interaction of LDH with anions of the intercellular and intracellular medium need to be considered, since such interaction can potentially disrupt ion transport, signaling processes, apoptosis, nutrition and proliferation of living cells. In the present paper molecular dynamics is used to determine the energies of interaction of organic anions (aspartic acid, glutamic acid and bicarbonate) with a fragment of layered double hydroxide Mg/Al-LDH. The average number of hydrogen bonds between the anions and the hydroxide surface and characteristic binding configurations are determined. Possible effects of LDH on the cell resulting from binding of protein fragments and replacement of native intracellular anions with delivered anions are considered.

  12. Energy and structure of bonds in the interaction of organic anions with layered double hydroxide nanosheets: A molecular dynamics study

    PubMed Central

    Tsukanov, A.A.; Psakhie, S.G.

    2016-01-01

    The application of hybrid and hierarchical nanomaterials based on layered hydroxides and oxyhydroxides of metals is a swiftly progressing field in biomedicine. Layered double hydroxides (LDH) possess a large specific surface area, significant surface electric charge and biocompatibility. Their physical and structural properties enable them to adsorb various kinds of anionic species and to transport them into cells. However, possible side effects resulting from the interaction of LDH with anions of the intercellular and intracellular medium need to be considered, since such interaction can potentially disrupt ion transport, signaling processes, apoptosis, nutrition and proliferation of living cells. In the present paper molecular dynamics is used to determine the energies of interaction of organic anions (aspartic acid, glutamic acid and bicarbonate) with a fragment of layered double hydroxide Mg/Al-LDH. The average number of hydrogen bonds between the anions and the hydroxide surface and characteristic binding configurations are determined. Possible effects of LDH on the cell resulting from binding of protein fragments and replacement of native intracellular anions with delivered anions are considered. PMID:26817816

  13. Compositional and Structural Control on Anion Sorption Capability of Layered Double Hydroxides (LDHS)

    SciTech Connect

    Y. Wang; H. Gao

    2006-03-16

    Layered double hydroxides (LDHs) have shown great promise as anion getters. In this paper, we demonstrate that the sorption capability of a LDH for a specific oxyanion can be greatly increased by appropriately manipulating material composition and structure. A large set of LDH materials have been synthesized with various combinations of metal cations, interlayer anions, and the molar ratios of divalent cation M(II) to trivalent cation M(III). The synthesized materials have then been tested systematically for their sorption capabilities for pertechnetate (TcO{sub 4}{sup -}). It is discovered that for a given interlayer anion (either CO{sub 3}{sup 2-} or NO{sub 3}{sup -}) the Ni-Al LDH with a Ni/Al ratio of 3:1 exhibits the highest sorption capability among all the materials tested. The distribution coefficient (K{sub d}) is determined to be as high as 307 mL/g for Ni{sub 6}Al{sub 2}(0H){sub 16}CO{sub 3}nH{sub 2}O and 1390 mL/g for Ni{sub 6}Al{sub 2}(OH){sub 16}NO{sub 3}nH{sub 2}O at a pH of 8. The sorption of TcO{sub 4}{sup -} on M(II)-M(III)-CO{sub 3} LDHs is dominated by the edge sites of LDH layers and strongly correlated with the basal spacing d{sub 003} of the materials, which increases with the decreasing radii of both divalent and trivalent cations. The sorption reaches its maximum when the layer spacing is just large enough for a pertechnetate anion to fit into a cage space between two neighboring octahedra of metal hydroxides at the edge. Furthermore, the sorption is found to increase with the crystallinity of the materials. For a given combination of metal cations and an interlayer anion, a best crystalline LDH material is obtained generally with a M(II)/M(III) ratio of 3:1. Replacement of interlayer carbonate with readily exchangeable nitrate greatly increases the sorption capability of a LDH material for pertechnetate, due to the enhanced adsorption on edge sites and the possible contribution from interlayer anion exchanges. The work reported here will

  14. DNA release from lipoplexes by anionic lipids: correlation with lipid mesomorphism, interfacial curvature, and membrane fusion

    SciTech Connect

    Tarahovsky, Yury S.; Koynova, Rumiana; MacDonald, Robert C.

    2010-01-18

    DNA release from lipoplexes is an essential step during lipofection and is probably a result of charge neutralization by cellular anionic lipids. As a model system to test this possibility, fluorescence resonance energy transfer between DNA and lipid covalently labeled with Cy3 and BODIPY, respectively, was used to monitor the release of DNA from lipid surfaces induced by anionic liposomes. The separation of DNA from lipid measured this way was considerably slower and less complete than that estimated with noncovalently labeled DNA, and depends on the lipid composition of both lipoplexes and anionic liposomes. This result was confirmed by centrifugal separation of released DNA and lipid. X-ray diffraction revealed a clear correlation of the DNA release capacity of the anionic lipids with the interfacial curvature of the mesomorphic structures developed when the anionic and cationic liposomes were mixed. DNA release also correlated with the rate of fusion of anionic liposomes with lipoplexes. It is concluded that the tendency to fuse and the phase preference of the mixed lipid membranes are key factors for the rate and extent of DNA release. The approach presented emphasizes the importance of the lipid composition of both lipoplexes and target membranes and suggests optimal transfection may be obtained by tailoring lipoplex composition to the lipid composition of target cells.

  15. Anion Effects on Interfacial Absorption of Gases in Ionic Liquids. A Molecular Dynamics Study

    SciTech Connect

    Wick, Collin D.; Dang, Liem X.

    2011-06-02

    Molecular dynamics simulations with many-body interactions were carried out to systematic study the effect of anion type, tetrafluoroborate [BF4] or hexafluorophosphate [PF6], paired with the cation 1-butyl-3-methylimidazolium [bmim], on the interfacial absorption of gases in room temperature ionic liquids (RTILs). The potentials of mean force (PMF) of CO2 and H2O at 350 K were calculated across the air-liquid interfaces of [bmim][BF4] and [bmim][PF6]. We found that the PMFs for H2O exhibited no interfacial minima at both interfaces, while the corresponding PMFs for CO2 had significant free energy minima there. However, the PMFs for H2O showed a much higher interfacial free energy than in the bulk for [bmim][BF4], but only a slightly higher interfacial free energy for [bmim][PF6] than in bulk. The reason for this was due to the more hydrophilic nature of the [BF4] anion, and the fact that [BF4] was found to have little propensity for the interface. Our results show that H2O is much more likely to be found at the air-[bmim][PF6] interface than at the air-[bmim][BF4] interface. The free energies of solvation were found to be more negative for [bmim][BF4] than [bmim][PF6] for water and similar for CO2. This observation is consistent with experimental Henry’s law coefficients. Our results show that anion type, in addition to affecting the free energy of solvation into RTILs, should also significantly influence the uptake mechanism. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  16. A molecular dynamic study of layered hydroxide induced depletion of mobile anions within the extracellular medium

    NASA Astrophysics Data System (ADS)

    Tsukanov, Alexey A.; Psakhie, Sergey G.

    2015-10-01

    The strong surface electric charge density of clay mineral host nanolayers enables their use as host-guest nanohybrids in many different areas of application. In particular, layered double hydroxides (LDH) of metals have found applications in medicine. Drug-LDH or gene-LDH nanohybrids are used for targeted delivery of biomedical agents to diseased cells or cancer cells. Fragments of the LDH host nanolayers may remain both within the cell and in the extracellular medium after drug delivery. How these charged nanosheets affect the cell electrostatics is still poorly understood. In the present paper, the idealized case of a single pure Mg2/Al-LDH nanolayer interacting with the extracellular anion environment was investigated to estimate the order of magnitude of a possible shift of the cell membrane equilibrium potential. An approximate dependence of the change in the chloride equilibrium membrane potential on the concentration of pure Mg2/Al-LDH nanosheets was determined.

  17. Rare earth and zinc layered hydroxide salts intercalated with the 2-aminobenzoate anion as organic luminescent sensitizer

    SciTech Connect

    Cursino, Ana Cristina Trindade; Rives, Vicente; Trujillano, Raquel

    2015-10-15

    Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide salts intercalated with nitrate anions were synthesized, followed by exchange with 2-aminobenzoate. The UV absorption ability was improved after intercalation/grafting in relation to that shown by the parent material. - Highlights: • Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide were synthesized. • Intercalated nitrate anions were exchanged by 2-aminobenzoate. • In all the 2-aminobenzoate containing compounds, the grafting reaction was detected. • The UV absorption ability was improved after the exchange reactions. • Rare earth hydroxide salts are potential matrixes to produce luminescent materials. - Abstract: Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide salts intercalated with nitrate anions were synthesized, followed by exchange with 2-aminobenzoate. The obtained compounds were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR) and ultraviolet visible (UV–vis) spectroscopies, fluorescence measurements and thermal analysis (TGA/DTA). The results from FTIR spectroscopy suggest a direct coordination of 2-aminobenzoate to the metal cations of the inorganic layered structure. The organic derivative products from the intercalation reactions absorb a broader range of UV-light in relation to that shown by the parent material; the photoluminescence measurements present a strong violet, blue and green luminescence under UV-light excitation for layered compounds with, Zn, Y and Tb, respectively. Rare earth hydroxide salts (RE-LHS) are potential alternative matrices for the immobilization of organic species to produce luminescent materials.

  18. 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.

  19. Photocatalytic O{sub 2} evolution from water over Zn–Cr layered double hydroxides intercalated with inorganic anions

    SciTech Connect

    Hirata, Naoya; Tadanaga, Kiyoharu; Tatsumisago, Masahiro

    2015-02-15

    Graphical abstract: The photocatalytic activity of Zn–Cr LDHs intercalated with various inorganic anions was studied by O{sub 2} evolution from aqueous solution of AgNO{sub 3} as a sacrificial agent. All the prepared LDHs showed photocatalytic activity under either UV and/or visible light irradiation. The interlayer anions affected the photocatalytic activity of the LDHs. - Highlights: • Zn–Cr layered double hydroxides intercalated with inorganic anions were synthesized. • Photocatalytic activity of the LDHs was studied by O{sub 2} evolution. • All the prepared LDHs showed photocatalytic activity under either UV and/or visible light irradiation. • The interlayer anions affected the photocatalytic activity of the LDHs. - Abstract: Zn–Cr layered double hydroxides (LDHs) intercalated with inorganic anions (CO{sub 3}{sup 2−}, Cl{sup −}, SO{sub 4}{sup 2−} and NO{sub 3}{sup −}) were synthesized by the co-precipitation method and the anion exchange process. The photocatalytic activity of the LDHs was studied by O{sub 2} evolution from aqueous solution of AgNO{sub 3} as a sacrificial agent. All the prepared LDHs showed photocatalytic activity under either UV and/or visible light irradiation. Besides, the interlayer anions affected the photocatalytic activity of the LDHs. After irradiation, Ag particles were formed on the LDHs by accepting the electrons generated during the photocatalytic reaction.

  20. Efficient defluoridation of water using reusable nanocrystalline layered double hydroxides impregnated polystyrene anion exchanger.

    PubMed

    Cai, Jianguo; Zhang, Yanyang; Pan, Bingcai; Zhang, Weiming; Lv, Lu; Zhang, Quanxing

    2016-10-01

    Water decontamination from fluoride is still a challenging task of global concern. Recently, Al-based layered double hydroxides (LDHs) have been extensively studied for specific fluoride adsorption from water. Unfortunately, they cannot be readily applied in scaled-up application due to their ultrafine particles as well as the regeneration issues caused by their poor stability at alkaline pHs. Here, we developed a novel (LDH)-based hybrid adsorbent, i.e., LALDH-201, by impregnating nanocrystalline Li/Al LDHs (LADLH) inside a commercial polystyrene anion exchanger D201. TEM image and XRD spectra of the resultant nanocomposite confirmed that the LDHs particles were nanosized inside the pores of D201 of highly crystalline nature and well-ordered layer structure. After impregnation, the chemical and mechanical stability of LALDH were significantly improved against pH variation, facilitating its application at a wide pH range (3.5-12). Fluoride adsorption onto LALDH-201 was compared to D201 and activated alumina, evidencing the preferable removal fluoride of LALDH-201. Fluoride adsorption onto LALDH-201 followed pseudo-second-order model, with the maximum capacity (62.5 mg/g from the Sips model) much higher than the other two adsorbents. Fixed-bed adsorption run indicated the qualified treatable volume of the fluoride contaminated groundwater (4.1 mg/L initially) with LALDH-201 was about 11 times as much as with the anion exchanger D201 when the breakthrough point was set as 1.5 mg/L. The capacity of LALDH-201 could be effectively refreshed for continuous column operation without observable loss by using the mixed solution of 0.01 M NaOH + 1 M NaCl. The above results suggested that the hybrid adsorbent LALDH-201 is very promising for water defluoridation in scaled-up application. PMID:27337346

  1. Efficient defluoridation of water using reusable nanocrystalline layered double hydroxides impregnated polystyrene anion exchanger.

    PubMed

    Cai, Jianguo; Zhang, Yanyang; Pan, Bingcai; Zhang, Weiming; Lv, Lu; Zhang, Quanxing

    2016-10-01

    Water decontamination from fluoride is still a challenging task of global concern. Recently, Al-based layered double hydroxides (LDHs) have been extensively studied for specific fluoride adsorption from water. Unfortunately, they cannot be readily applied in scaled-up application due to their ultrafine particles as well as the regeneration issues caused by their poor stability at alkaline pHs. Here, we developed a novel (LDH)-based hybrid adsorbent, i.e., LALDH-201, by impregnating nanocrystalline Li/Al LDHs (LADLH) inside a commercial polystyrene anion exchanger D201. TEM image and XRD spectra of the resultant nanocomposite confirmed that the LDHs particles were nanosized inside the pores of D201 of highly crystalline nature and well-ordered layer structure. After impregnation, the chemical and mechanical stability of LALDH were significantly improved against pH variation, facilitating its application at a wide pH range (3.5-12). Fluoride adsorption onto LALDH-201 was compared to D201 and activated alumina, evidencing the preferable removal fluoride of LALDH-201. Fluoride adsorption onto LALDH-201 followed pseudo-second-order model, with the maximum capacity (62.5 mg/g from the Sips model) much higher than the other two adsorbents. Fixed-bed adsorption run indicated the qualified treatable volume of the fluoride contaminated groundwater (4.1 mg/L initially) with LALDH-201 was about 11 times as much as with the anion exchanger D201 when the breakthrough point was set as 1.5 mg/L. The capacity of LALDH-201 could be effectively refreshed for continuous column operation without observable loss by using the mixed solution of 0.01 M NaOH + 1 M NaCl. The above results suggested that the hybrid adsorbent LALDH-201 is very promising for water defluoridation in scaled-up application.

  2. One-step synthesis of layered yttrium hydroxides in immiscible liquid–liquid systems: Intercalation of sterically-bulky hydrophobic organic anions and doping of europium ions

    SciTech Connect

    Watanabe, Mebae; Fujihara, Shinobu

    2014-02-15

    Inorganic–organic layered rare-earth compounds were synthesized on the basis of a biphasic liquid–liquid system in one pot. Layered yttrium hydroxides (LYHs) were chosen as a host material for the intercalation of hydrophobic organic guest anions such as benzoate, sebacate, or laurate. In a typical synthesis, an organic phase dissolving carboxylic acid was placed in contact with an equal amount of an aqueous phase dissolving yttrium nitrate n-hydrate and urea. At elevated temperatures up to 80 °C, urea was hydrolyzed to release hydroxyl anions which were used to form yttrium hydroxide layers. LYHs were then precipitated with the intercalation of carboxylate anions delivered from the organic phase under the distribution law. The structure and the morphology of the LYHs could be modulated by the intercalated anions. Doped with Eu{sup 3+} ions, the LYHs exhibited red photoluminescence which was enhanced by the intercalated anions due to the antenna effect. - Graphical abstract: The Eu{sup 3+}-doped layered yttrium hydroxide exhibits intense red photoluminescence after intercalation of benzoate ions. Display Omitted - Highlights: • Immiscible biphasic liquid systems were introduced to synthesize layered yttrium hydroxides. • The temperature of the biphasic systems does not exceed 80 °C in one step of the synthesis. • Hydrophobic organic anions were intercalated between the hydroxide layers in one pot. • Structure and morphology of the hydroxides were modulated by changing the kind of organic anions. • Eu{sup 3+}-doping led to red luminescence from the hydroxides in association with the intercalated organic anions.

  3. Ultrasonically-enhanced mechanochemical synthesis of CaAl-layered double hydroxides intercalated by a variety of inorganic anions.

    PubMed

    Szabados, Márton; Mészáros, Rebeka; Erdei, Szabolcs; Kónya, Zoltán; Kukovecz, Ákos; Sipos, Pál; Pálinkó, István

    2016-07-01

    CaAl-layered double hydroxides (CaAl-LDHs) were synthesised with various interlayer anions (CO3(2-), F(-), Cl(-), Br(-) and I(-)) by mechanochemical pre-treatment followed by ultrasonic irradiation in aqueous media. The parameters of the syntheses (duration of pre-milling and sonication, quality of the aqueous media, temperature) were altered in order to optimise the procedure and to understand the formation of LDH and other secondary products. The products were characterised by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The optimisation resulted in close-to-phase-pure CaAl-LDHs, not only with carbonate and chloride interlayer anions, but the hard-to-intercalate bromide and iodide as well.

  4. Synthesis and photoluminescence properties of europium doped Mg-Al layered double hydroxides intercalated with MoO anions

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Pan, Qingrui; Liu, Qi; He, Yang; Mann, Tom; Li, Rumin; Zhang, Milin; Liu, Lianhe

    2012-05-01

    Novel fluorescent Eu-containing layered double hydroxides (Eu-LDHs) were prepared by direct ion-exchange of EuMgAl-NO3 LDHs precursors with MoO anions. The samples were characterized by elemental analyses, powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Raman spectra, photoluminescence spectroscopy. The results indicated that Eu3+ ions were likely incorporated into the hydrotalcite lattice and MoO anions were successfully intercalated into interlayer region of the LDHs with the Mo/Al molar ratio close to 0.40. The luminescence properties were largely enhanced compared with the EuMgAl-NO3 LDHs precursors, which were attributed to the energy transfer between Eu3+ and MoO.

  5. Protonation of a hydroxide anion bridging two divalent magnesium cations in water probed by first-principles metadynamics simulation.

    PubMed

    Park, Jung Mee; Boero, Mauro

    2010-09-01

    The protonation of a hydroxide anion (OH(-)) located between two magnesium cations (Mg(2+)) in aqueous solution has been investigated by first-principles metadynamics simulation. We observe that the complex Mg(2+)-OH(-)-Mg(2+) is stabilized by the coparticipation of the hydroxide anion to the first hydration shells of both the Mg(2+) cations. Contrary to the cases of OH(-) in pure water, the transfer of protons in the presence of the divalent metal ions turns out to be a slow chemical event. This can be ascribed to the decreased proton affinity of the bridging OH(-). Metadynamics simulation, used to overcome the difficulty of the long time scale required by the protonation of the bridging OH(-), has shown that the system possesses a great stability on the reactant state, characterized by a bioctahedral (6,6) solvation structure around the two Mg(2+) cations. The exploration of the free energy landscape shows that this stable bioctahedral configuration converts into a lower coordinated (5,6) structure, leading to a proton transfer from a water molecule belonging to the first solvation shell of the Mg(2+) ion having the lower coordination to the bridging OH(-); the free energy barrier for the protonation reaction is 11 kcal/mol, meaning that the bridging hydroxide is a weak base. During the proton transfer, the bridging OH(-) reverts to an H(2)O molecule, and this breaks the electrostatic coupling of the two Mg(2+) ions, which depart independently with their own hydration shells, one of which is entirely formed by water molecules. The second one carries the newly created OH(-). Our results show that the flexibility in the metal coordination plays a crucial role in both the protonation process of the bridging OH(-) and the separation of the metal cations, providing useful insight into the nature of proton transfer in binuclear divalent metal ions, with several biological implications, such as, for instance, transesterification of catalytic RNA.

  6. Nanoporous hollow transition metal chalcogenide nanosheets synthesized via the anion-exchange reaction of metal hydroxides with chalcogenide ions.

    PubMed

    Zhao, Weiwei; Zhang, Chao; Geng, Feiyang; Zhuo, Sifei; Zhang, Bin

    2014-10-28

    Nanoporous hollow transition metal chalcogenides are of special interest for a variety of promising applications. Although some advanced synthetic methods have been reported, the development of a facile and general strategy to fabricate porous hollow nanostructures of transition metal chalcogenides, especially with enhanced electrocatalytic performance, still remains highly challenged. Herein, we report a facile chemical transformation strategy to prepare nanoporous hollow Co3S4 nanosheets via the anion exchange reaction of Co(OH)2 with sulfide ions. The chemical transformation mechanism involves the as-formed layer of nanoporous cobalt sulfide on Co(OH)2 driven by the anion-exchange-reaction and lattice mismatch induced quick strain release, a following diffusion-effect-dominated core-shell hollow intermediate with hollow interiors, and subsequent Ostwald ripening growth of hollow nanosheets at elevated temperatures. This anion-exchange strategy of transition metal hydroxides with chalcogenide ions is also suitable for fabricating nanoporous hollow nanosheets of other metal chalcogenides (e.g., CoSe2, CoTe2, CdS, and NiS). The as-prepared nanoporous hollow Co3S4 nanosheets are found to be highly active and stable for electrocatalytic oxygen evolution reaction.

  7. Sugar-anionic clay composite materials: intercalation of pentoses in layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Aisawa, Sumio; Hirahara, Hidetoshi; Ishiyama, Kayoko; Ogasawara, Wataru; Umetsu, Yoshio; Narita, Eiichi

    2003-09-01

    The intercalation of non-ionized guest pentoses (ribose and 2-deoxyribose) into the Mg-Al and Zn-Al layered double hydroxides (LDHs) was carried out at 298 K by the calcination-rehydration reaction using the Mg-Al and Zn-Al oxide precursors calcined at 773 K. The resulting solid products reconstructed the LDH structure with incorporating pentoses, and the maximum amount of ribose intercalated by the Mg-Al oxide precursor was approximately 20 times that by the Zn-Al oxide precursor. The ribose/Mg-Al LDH was observed to have the expanded LDH structure with a broad (003) spacing of 0.85 nm. As the thickness of the LDH hydroxide basal layer is 0.48 nm, the interlayer distance of the ribose/Mg-Al LDH is 0.37 nm. This value corresponds to molecular size of ribose in thickness (0.36 nm), supporting that ribose is horizontally oriented in the interlayer space of LDH. The maximum amount of ribose intercalated by the Mg-Al oxide precursor was approximately 5 times that of 2-deoxyribose. Ribose is substituted only by the hydroxyl group at C-2 position for 2-deoxyribose. Therefore, the number of hydroxyl group of sugar is essentially important for the intercalation of sugar molecule into the LDH, suggesting that the intercalation behavior of sugar for the LDH was greatly influenced by hydrogen bond between hydroxyl group of the intercalated pentose and the LDH hydroxide basal layers.

  8. Layered double hydroxide/polyethylene terephthalate nanocomposites. Influence of the intercalated LDH anion and the type of polymerization heating method

    SciTech Connect

    Herrero, M.; Martinez-Gallegos, S.; Labajos, F.M.; Rives, V.

    2011-11-15

    Conventional and microwave heating routes have been used to prepare PET-LDH (polyethylene terephthalate-layered double hydroxide) composites with 1-10 wt% LDH by in situ polymerization. To enhance the compatibility between PET and the LDH, terephthalate or dodecyl sulphate had been previously intercalated in the LDH. PXRD and TEM were used to detect the degree of dispersion of the filler and the type of the polymeric composites obtained, and FTIR spectroscopy confirmed that the polymerization process had taken place. The thermal stability of these composites, as studied by thermogravimetric analysis, was enhanced when the microwave heating method was applied. Dodecyl sulphate was more effective than terephthalate to exfoliate the samples, which only occurred for the terephthalate ones under microwave irradiation. - Graphical abstract: Conventional and microwave heating routes were used to prepare PET-LDH (polyethylene terephthalate-layered double hydroxide) composites with 1-10 wt% LDH by in situ polymerization. To enhance the compatibility between PET and the LDH, terephthalate or dodecyl sulphate was previously intercalated into the LDH. The microwave process improves the dispersion and the thermal stability of nanocomposites due to the interaction of the microwave radiation and the dipolar properties of EG and the homogeneous heating. Highlights: > LDH-PET compatibility is enhanced by preintercalation of organic anions. > Dodecylsulphate performance is much better than that of terephthalate. > Microwave heating improves the thermal stability of the composites. > Microwave heating improves as well the dispersion of the inorganic phase.

  9. Leaching of iodide (I(-)) and iodate (IO3(-)) anions from synthetic layered double hydroxide materials.

    PubMed

    Theiss, Frederick L; Ayoko, Godwin A; Frost, Ray L

    2016-09-15

    Several studies have previously demonstrated that layered double hydroxides (LDHs) show considerable potential for the adsorption of radioiodine from aqueous solution; however, few studies have demonstrated that these materials are able to store radioactive (131)I for an acceptable period. The leaching of iodide (I(-)) and iodate (IO3(-)) form Mg/Al LDHs has been carried out. Contact time appeared to be a more significant variable for the leaching of iodate (IO3(-)) compared to that of iodide (I(-)). Experimental results are fitted to the pseudo second order model, suggesting that diffusion is likely to be the rate-limiting step. The presence of carbonate in the leaching solution appeared to significantly increase the leaching of iodide (I(-)) as did the presence of chloride to a lesser extent. The maximum amount of iodate (IO3(-)) leached using ultrapure water as the leaching solution was 21% of the iodate (IO3(-)) originally present. The corresponding result for iodide (I(-)) was even lower at 3%.

  10. Interlayer intercalation and arrangement of 2-mercaptobenzothiazolate and 1,2,3-benzotriazolate anions in layered double hydroxides: In situ X-ray diffraction study

    NASA Astrophysics Data System (ADS)

    Serdechnova, Maria; Salak, Andrei N.; Barbosa, Filipe S.; Vieira, Daniel E. L.; Tedim, João; Zheludkevich, Mikhail L.; Ferreira, Mário G. S.

    2016-01-01

    2-mercaptobenzothiazole (MBT) and 1,2,3-benzotriazole (BTA) are very promising inhibitors for the corrosion protection of aluminum alloys. These inhibitors can be incorporated in protective coatings in the form of anions intercalated into interlayers of layered double hydroxides (LDHs). Capacity and performance of such LDH-nanocontainers depend on the arrangement of the anions in their interlayers. In this work, intercalation of MBT- and BTA- into Mg-Al-NO3 and Zn-Al-NO3 LDHs were studied in detail using X-ray diffraction (XRD) methods including in situ XRD. The nitrate-to-MBT(BTA) anion exchange is much faster than considered previously. Well-formed Mg-Al-MBT, Zn-Al-MBT, Mg-Al-BTA LDHs were obtained after a 20-min exchange reaction at pH 11.5 at room temperature. It was demonstrated that Zn-Al-BTA LDH cannot be obtained under the same conditions due to the reaction between BTA and the Zn-Al hydroxide layers. Substitution of nitrates by organic anions occurs with the participation of hydroxide anions. Although no intermediate LDH phase intercalated with the combination of NO3 - and OH- appears, formation of the LDH-MBT and LDH-BTA phases results also in appearance of an LDH phase intercalated with OH- at the final stage of the anion exchange. In the LDH interlayer, MBT- and BTA- form a double layer in which these species have a tilted orientation against the layer plane (herringbone-like arrangement). Such an arrangement meets the LDH layer-interlayer electroneutrality and matches well with the observed values of the layer-interlayer distance.

  11. Characterization and film properties of electrophoretically deposited nanosheets of anionic titanate and cationic MgAl-layered double hydroxide.

    PubMed

    Matsuda, Atsunori; Sakamoto, Hisatoshi; Mohd Nor, Mohd Arif Bin; Kawamura, Go; Muto, Hiroyuki

    2013-02-14

    Anionic hydrated titanate (H(n)TiO(m): HTO) nanosheets and cationic magnesium-aluminum layered double hydroxide (Mg-Al LDH) nanosheets were electrophoretically deposited on positively and negatively charged indium tin oxide (ITO)-coated glass substrates, respectively. The HTO nanosheets and Mg-Al LDH nanosheets obtained were identified in neutral water as H(2)Ti(4)O(9)·nH(2)O with a ζ-potential of -23 mV and Mg(6)Al(2)(OH)(18)·4.5H(2)O with a ζ-potential of +41 mV, respectively. Dense and smooth HTO and Mg-Al LDH films with layered structures with thicknesses of about 10-15 μm were prepared in 300 s at 7.5 V by electrophoretic deposition (EPD) from the nanosheet suspensions. Both EPD HTO and LDH films showed elasticity because of their layered laminate structures. The HTO thick films demonstrated large adsorption properties and high photocatalytic activity, while the Mg-Al LDH thick films showed relatively high ionic conductivity of 10(-5) S cm(-1) at 80 °C and 80% relative humidity.

  12. Enhancing removal efficiency of anionic dye by combination and calcination of clay materials and calcium hydroxide.

    PubMed

    Vimonses, Vipasiri; Jin, Bo; Chow, Christopher W K; Saint, Chris

    2009-11-15

    We explored a feasible approach to enhance removal capacity of three natural clays for removing anionic dye from aqueous solution. Optimal mixing proportions of the clay materials and temperature range for the calcination were investigated. We found that the removal efficiency can be improved significantly when the clay materials were mixed at certain ratio with the addition of lime and the mixed clay materials were calcined 100-300 degrees C. Batch experiments were conducted to study the effects of initial concentration, material dosage, contact time and pH on dye elimination. Kinetic study showed that more than 80% dye removal took place in 5 min. A high removal capacity (>575 mg g(-1)) of the mixed clay materials can be achieved at a low adsorbent dose. The mixed clay materials can be easily recovered by thermal treatment. The recovered mixtures demonstrated an enhanced removal capability after a few cycles of removal and regeneration. The results revealed that use of these clay materials could develop a low-cost treatment process for industrial wastewater. PMID:19604637

  13. Synthesis and anion exchange properties of a Zn/Ni double hydroxide salt with a guarinoite structure

    SciTech Connect

    Delorme, F.; Seron, A.; Licheron, M.; Veron, E.; Giovannelli, F.; Beny, C.; Jean-Prost, V.; Martineau, D.

    2009-09-15

    In this study, the first route to synthesize a compound with the guarinoite structure (Zn,Co,Ni){sub 6}(SO{sub 4})(OH,Cl){sub 10}.5H{sub 2}O is reported. Zn/Ni guarinoite is obtained from the reaction of NiSO{sub 4}.7H{sub 2}O with solid ZnO in aqueous solution. The resulting green Zn/Ni guarinoite ((Zn{sub 3.52}Ni{sub 1.63})(SO{sub 4}){sub 1.33}(OH{sub 7.64}).4.67H{sub 2}O) was characterized by X-ray diffraction, infrared spectrometry, UV-Visible spectrometry and thermal analysis. It is shown that its structure is similar to the one described for the layered Zn sulfate hydroxide hydrate, i.e. brucite layers with 1/4 empty octahedra presenting tetrahedrally coordinated divalent atoms above and below the empty octahedra. Ni atoms are located in the octahedra and zinc atoms in tetrahedra and octahedra. In this structure the exchangeable anions are located at the apex of tetrahedra. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations show that the Zn/Ni guarinoite is composed of aggregates of hexagonal plates of several hundreds of nanometers. Due to its interest for industrial or environmental applications, the exchange of sulfate groups by carbonates has been investigated. Results show a limited exchange and a higher affinity of the Zn/Ni guarinoite for sulfates compared to carbonates. - Graphical abstract: SEM micrograph (secondary electrons) of the synthesized Zn/Ni guarinoite showing that aggregates are composed of small plate-like particles.

  14. Growth of PbTe nanorods controlled by polymerized tellurium anions and metal(II) amides via composite-hydroxide-mediated approach

    SciTech Connect

    Wan Buyong; Hu Chenguo; Liu Hong; Xiong Yufeng; Li Feiyun; Xi Yi; He Xiaoshan

    2009-09-15

    The pure face-centered-cubic PbTe nanorods have been synthesized by the composite-hydroxide-mediated approach using hydrazine as a reducing agent. The method is based on reaction among reactants in the melts of potassium hydroxide and sodium hydroxide eutectic at 170-220 deg. C and normal atmosphere without using any organic dispersant or surface-capping agent. Scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy were used to characterize the structure, morphology and composition of the samples. The diameters of nanorods are almost fixed, while the lengths can be tunable under different growth time and temperatures. The growth mechanism of PbTe nanorods is investigated via UV-vis absorption, demonstrating that polymerized tellurium anions and metal(II) amides in the hydrazine hydroxide melts could control the crystallization and growth process of PbTe nanostructures. The band gap of as-synthesized PbTe nanorods has been calculated based on UV-vis-NIR optical diffuse reflectance spectra data.

  15. Intercalation of p-methycinnamic acid anion into Zn-Al layered double hydroxide to improve UV aging resistance of asphalt

    SciTech Connect

    Peng, Chao; Dai, Jing; Yu, Jianying; Yin, Jian

    2015-02-15

    A UV absorber, p-methycinnamic acid (PMCA), was intercalated into Zn-Al layered double hydroxide (LDH) by calcination recovery. Fourier transform infrared spectroscopy showed that the PMCA anions completely replaced the CO{sub 3}{sup 2−} anions in the interlayer galleries of Zn-Al-LDH containing PMCA anions (Zn-Al-PMCA-LDH). X-ray diffraction and transmission electron microscopy showed that the interlayer distance increased from 0.78 nm to 1.82 nm after the substitution of PMCA anions for CO{sub 3}{sup 2−} anions. The similar diffraction angles of the CO{sub 3}{sup 2−} anion-containing Zn-Al-LDH (Zn-Al-CO{sub 3}{sup 2−}-LDH) and the Zn-Al-CO{sub 3}{sup 2−}-LDH/styrene–butadiene–styrene (SBS) modified asphalt implied that the asphalt molecules do not enter into the LDH interlayer galleries to form separated-phase structures. The different diffraction angles of Zn-Al-PMCA-LDH and Zn-Al-PMCA-LDH/SBS modified asphalt indicated that the asphalt molecules penetrated into the LDH interlayer galleries to form an expanded-phase structure. UV-Vis absorbance analyses showed that Zn-Al-PMCA-LDH was better able to block UV light due to the synergistic effects of PMCA and Zn-Al-LDH. Conventional physical tests and atomic force microscopy images of the SBS modified asphalt, Zn-Al-CO{sub 3}{sup 2−}-LDH/SBS modified asphalt and Zn-Al-PMCA-LDH/SBS modified asphalt before and after UV aging indicated that Zn-Al-PMCA-LDH improved the UV aging resistance of SBS modified asphalts.

  16. Preparing alkaline anion exchange membrane with enhanced hydroxide conductivity via blending imidazolium-functionalized and sulfonated poly(ether ether ketone)

    NASA Astrophysics Data System (ADS)

    Li, Zhen; Jiang, Zhongyi; Tian, Huimin; Wang, Siwen; Zhang, Bei; Cao, Ying; He, Guangwei; Li, Zongyu; Wu, Hong

    2015-08-01

    The development of alkaline anion exchange membrane (AEM) with both high ion conductivity and stabilities is of great significance for fuel cell applications. In this study, a facile acid-base blending method is designed to improve AEM performances. Basic imidazolium-functionalized poly (ether ether ketone) with a high functionalization degree is employed as polymer matrix to pursue high ion-exchange capacity (IEC) as well as high hydroxide conductivity, meanwhile acidic sulfonated poly (ether ether ketone) (SPEEK) is employed as the cross-linking agent to enhance the stabilities of the blend membranes. Particularly, an in-situ Menshutkin/crosslinking method is exploited to prevent the flocculation in the preparation process of blend membranes. As a result, dense and defect-free blend membranes are obtained. The blend membranes exhibit high level of IEC up to 3.15 mmol g-1, and consequently possess elevated hydroxide conductivity up to 31.59 mS cm-1 at 30 °C. In addition, benefiting from the strong electrostatic interaction introduced by the acid-base blending, the stabilities and methanol resistance of blend membranes are enhanced.

  17. Incorporation of transition metals into Mg-Al layered double hydroxides: Coprecipitation of cations vs. their pre-complexation with an anionic chelator

    SciTech Connect

    Tsyganok, Andrey; Sayari, Abdelhamid . E-mail: Abdel.Sayari@science.uottawa.ca

    2006-06-15

    A comparative study on two different methods for preparing Mg-Al layered double hydroxides (LDH) containing various divalent transition metals M (M=Co, Ni, Cu) has been carried out. The first (conventional) method involved coprecipitation of divalent metals M(II) with Mg(II) and Al(III) cations using carbonate under basic conditions. The second approach was based on the ability of transition metals to form stable anionic chelates with edta{sup 4-} (edta{sup 4-}=ethylenediaminetetraacetate) that were synthesized and further introduced into LDH by coprecipitation with Mg and Al. The synthesized LDHs were characterized by X-ray diffraction (XRD) and X-ray fluorescence (XRF) methods, thermogravimetry with mass-selective detection of decomposition products (TG-MSD), Fourier transform infrared (FTIR) and Raman spectroscopy techniques. The results obtained were discussed in terms of efficiency of transition metal incorporation into the LDH structure, thermal stability of materials and the ability of metal chelates to intercalate the interlayer space of Mg-Al LDH. Vibrational spectroscopy studies confirmed that the integrity of the metal chelates was preserved upon incorporation into the LDH. - Graphical abstract: Two ways for introducing transition metals M(II) into Mg-Al layered double hydroxides (MY{sup 2-} denotes the edta chelate of transition metal M(II)).0.

  18. Anionic clay as the drug delivery vehicle: tumor targeting function of layered double hydroxide-methotrexate nanohybrid in C33A orthotopic cervical cancer model.

    PubMed

    Choi, Goeun; Piao, Huiyan; Alothman, Zeid A; Vinu, Ajayan; Yun, Chae-Ok; Choy, Jin-Ho

    2016-01-01

    Methotrexate (MTX), an anticancer agent, was successfully intercalated into the anionic clay, layered double hydroxides to form a new nanohybrid drug. The coprecipitation and subsequent hydrothermal method were used to prepare chemically, structurally, and morphologically well-defined two-dimensional drug-clay nanohybrid. The resulting two-dimensional drug-clay nanohybrid showed excellent colloidal stability not only in deionized water but also in an electrolyte solution of Dulbecco's Modified Eagle's Medium with 10% fetal bovine serum, in which the average particle size in colloid and the polydispersity index were determined to be around 100 and 0.250 nm, respectively. The targeting property of the nanohybrid drug was confirmed by evaluating the tumor-to-blood and tumor-to-liver ratios of the MTX with anionic clay carrier, and these ratios were compared to those of free MTX in the C33A orthotopic cervical cancer model. The biodistribution studies indicated that the mice treated with the former showed 3.5-fold higher tumor-to-liver ratio and fivefold higher tumor-to-blood ratio of MTX than those treated with the latter at 30 minutes postinjection.

  19. Anionic clay as the drug delivery vehicle: tumor targeting function of layered double hydroxide-methotrexate nanohybrid in C33A orthotopic cervical cancer model

    PubMed Central

    Choi, Goeun; Piao, Huiyan; Alothman, Zeid A; Vinu, Ajayan; Yun, Chae-Ok; Choy, Jin-Ho

    2016-01-01

    Methotrexate (MTX), an anticancer agent, was successfully intercalated into the anionic clay, layered double hydroxides to form a new nanohybrid drug. The coprecipitation and subsequent hydrothermal method were used to prepare chemically, structurally, and morphologically well-defined two-dimensional drug-clay nanohybrid. The resulting two-dimensional drug-clay nanohybrid showed excellent colloidal stability not only in deionized water but also in an electrolyte solution of Dulbecco’s Modified Eagle’s Medium with 10% fetal bovine serum, in which the average particle size in colloid and the polydispersity index were determined to be around 100 and 0.250 nm, respectively. The targeting property of the nanohybrid drug was confirmed by evaluating the tumor-to-blood and tumor-to-liver ratios of the MTX with anionic clay carrier, and these ratios were compared to those of free MTX in the C33A orthotopic cervical cancer model. The biodistribution studies indicated that the mice treated with the former showed 3.5-fold higher tumor-to-liver ratio and fivefold higher tumor-to-blood ratio of MTX than those treated with the latter at 30 minutes postinjection. PMID:26855572

  20. Ionic association of hydroperoxide anion HO2- in the binding mean spherical approximation. Spectroscopic study of hydrogen peroxide in concentrated sodium hydroxide solutions.

    PubMed

    Chlistunoff, Jerzy; Simonin, Jean-Pierre

    2006-12-28

    The ultraviolet-visible (UV-vis) spectroscopy of hydrogen peroxide in concentrated sodium hydroxide solutions was studied. The peroxide band in the UV range shifts from approximately 214 nm to approximately 236 nm as the NaOH concentration increases from 0.338 mol dm-3 to 13.1 mol dm-3. The band originates from an intramolecular electronic transition of the hydroperoxide anion HO2-, as indicated by the negligible temperature effect on the band position and confirmed by ab initio quantum mechanical calculations. It is postulated that the bathochromic shift of the peroxide band that accompanies the increase in NaOH concentration originates from the formation of the ion pair (Na+HO2-). The equilibrium constant for the ion association reaction (0.048 mol-1 dm3) and the characteristics of the individual absorption bands of the hydroperoxide anion and its associate with Na+ were determined from the numerical modeling of the absorbance data, using the binding mean spherical approximation (BIMSA).

  1. Luminescent ultrathin film of anionic styrylbiphenyl derivative-layered double hydroxide and its reversible sensing for heavy metal ions.

    PubMed

    Yan, Dongpeng; Lu, Jun; Wei, Min; Li, Shuangde; Evans, David G; Duan, Xue

    2012-06-28

    Ordered ultrathin films (UTFs) with blue luminescence based on a styrylbiphenyl derivative (BTBS) and Mg-Al-layered double hydroxide (LDH) nanosheets have been constructed employing the layer-by-layer assembly technique. UV-visible absorption and fluorescence spectroscopy showed a stepwise and regular growth of the films upon increasing the number of deposition cycles. XRD, AFM and SEM indicated that the films possess a periodic layered structure with a period of ca. 1.5 nm, and uniform surface morphology. The film thickness can be precisely controlled in the range ca. 15-53 nm. The BTBS-LDH UTFs exhibit improved UV-light resistance capability compared with the pristine BTBS and show well-defined polarized photoemission, with anisotropy of ca. 0.24. The UTFs show a fast, selective and reversible luminescent response to aqueous solutions containing different heavy metal ions, with the most significant luminescent quenching occurring for the Hg(2+) solution, shedding light on the fact that these films can serve as a new type of selective solid luminescent metal-ion sensor.

  2. Luminescent ultrathin film of anionic styrylbiphenyl derivative-layered double hydroxide and its reversible sensing for heavy metal ions.

    PubMed

    Yan, Dongpeng; Lu, Jun; Wei, Min; Li, Shuangde; Evans, David G; Duan, Xue

    2012-06-28

    Ordered ultrathin films (UTFs) with blue luminescence based on a styrylbiphenyl derivative (BTBS) and Mg-Al-layered double hydroxide (LDH) nanosheets have been constructed employing the layer-by-layer assembly technique. UV-visible absorption and fluorescence spectroscopy showed a stepwise and regular growth of the films upon increasing the number of deposition cycles. XRD, AFM and SEM indicated that the films possess a periodic layered structure with a period of ca. 1.5 nm, and uniform surface morphology. The film thickness can be precisely controlled in the range ca. 15-53 nm. The BTBS-LDH UTFs exhibit improved UV-light resistance capability compared with the pristine BTBS and show well-defined polarized photoemission, with anisotropy of ca. 0.24. The UTFs show a fast, selective and reversible luminescent response to aqueous solutions containing different heavy metal ions, with the most significant luminescent quenching occurring for the Hg(2+) solution, shedding light on the fact that these films can serve as a new type of selective solid luminescent metal-ion sensor. PMID:22491140

  3. 8-Anilino-1-naphthalenesulfonate/Layered Double Hydroxide Ultrathin Films: Small Anion Assembly and Its Potential Application as a Fluorescent Biosensor.

    PubMed

    Zhang, Ping; Li, Ling; Zhao, Yun; Tian, Zeyun; Qin, Yumei; Lu, Jun

    2016-09-01

    The fluorescent dye 8-anilino-1-naphthalenesulfonate (ANS) is a widely used fluorescent probe molecule for biochemistry analysis. This paper reported the fabrication of ANS/layered double hydroxide nanosheets (ANS/LDH)n ultrathin films (UTFs) via the layer-by-layer small anion assembly technique based on electrostatic interaction and two possible weak interactions: hydrogen-bond and induced electrostatic interactions between ANS and positive-charged LDH nanosheets. The obtained UTFs show a long-range-ordered periodic layered stacking structure and weak fluorescence in dry air or water, but it split into three narrow strong peaks in a weak polarity environment induced by the two-dimensional (2D) confinement effect of the LDH laminate; the fluorescence intensity increases with decreasing the solvent polarity, concomitant with the blue shift of the emission peaks, which show good sensoring reversibility. Meanwhile, the UTFs exhibit selective fluorescence enhancement to the bovine serum albumin (BSA)-like protein biomolecules, and the rate of fluorescence enhancement with the protein concentration is significantly different with the different protein aggregate states. The (ANS/LDH)n UTF has the potential to be a novel type of biological flourescence sensor material. PMID:27513829

  4. Influence of the anions on the N-cationic benzethonium salts in the solid state and solution: Chloride, bromide, hydroxide and citrate hydrates

    NASA Astrophysics Data System (ADS)

    Paradies, Henrich H.; Reichelt, Hendrik

    2016-06-01

    The crystal structures of the hydrated cationic surfactant benzethonium (Bzth) chloride, bromide, hydroxide, and citrate have been determined by X-ray diffraction analysis and compared with their structures in solution well above their critical micelle concentration. The differences in the nature of the various anions of the four Bzth-X materials lead to unique anion environments and 3-D molecular arrangements. The water molecule in the monoclinic Bzth-Cl or Bzth-Br forms is hydrogen bonded to the halides and particularly to the hydrogens of the methoxy groups of the Bzth moiety notwithstanding the weak Brønsted acidity of the methoxy hydrogens. The citrate strongly interacts with the hydrogens of the methoxy group forming an embedded anionic spherical cluster of a radius of 2.6 Å. The Bzth-OH crystallizes in a hexagonal lattice with two water molecules and reveals free water molecules forming hydrogen bonded channels through the Bzth-OH crystal along the c-axis. The distances between the cationic nitrogen and the halides are 4.04 Å and 4.20 Å, significantly longer than expected for typical van der Waals distances of 3.30 Å. The structures show weakly interacting, alternating apolar and polar layers, which run parallel to the crystallographic a-b planes or a-c planes. The Bzth-X salts were also examined in aqueous solution containing 20% (v/v) ethanol and 1.0 % (v/v) glycerol well above their critical micelle concentration by small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The [1,1,1] planes for the Bzth Cl or Br, the [0,0,2] and [1,1,0] planes for the Bzth-citrate, the [2,-1,0] planes and the [0,0,1] planes for the Bzth-OH found in the crystalline phase were also present in the solution phase, accordingly, the preservation of these phases are a strong indication of periodicity in the solution phase.

  5. Aluminum Hydroxide and Magnesium Hydroxide

    MedlinePlus

    Aluminum Hydroxide, Magnesium Hydroxide are antacids used together to relieve heartburn, acid indigestion, and upset stomach. They ... They combine with stomach acid and neutralize it. Aluminum Hydroxide, Magnesium Hydroxide are available without a prescription. ...

  6. Hydrated interfacial ions and electrons.

    PubMed

    Abel, Bernd

    2013-01-01

    Charged particles such as hydrated ions and transient hydrated electrons, the simplest anionic reducing agents in water, and the special hydronium and hydroxide ions at water interfaces play an important role in many fields of science, such as atmospheric chemistry, radiation chemistry, and biology, as well as biochemistry. This article focuses on these species near hydrophobic interfaces of water, such as the air or vacuum interface of water or water protein/membrane interfaces. Ions at interfaces as well as solvated electrons have been reviewed frequently during the past decade. Although all species have been known for some time with seemingly familiar features, recently the picture in all cases became increasingly diffuse rather than clearer. The current account gives a critical state-of-the art overview of what is known and what remains to be understood and investigated about hydrated interfacial ions and electrons.

  7. The interfacial lipid binding site on the potassium channel KcsA is specific for anionic phospholipids.

    PubMed

    Marius, Phedra; Alvis, Simon J; East, J Malcolm; Lee, Anthony G

    2005-12-01

    Lipid binding to the potassium channel KcsA from Streptomyces lividans has been studied using quenching of the fluorescence of Trp residues by brominated phospholipids. It is shown that binding of phospholipids to nonannular lipid binding sites on KcsA, located one each at the four protein-protein interfaces in the tetrameric structure, is specific for anionic phospholipids, zwitterionic phosphatidylcholine being unable to bind at the sites. The binding constant for phosphatidylglycerol of 3.0 +/- 0.7 mol fraction(-1) means that in a membrane containing approximately 20 mol% phosphatidylglycerol, as in the Escherichia coli inner membrane, the nonannular sites will be approximately 37% occupied by phosphatidylglycerol. The binding constant for phosphatidic acid is similar to that for phosphatidylglycerol but binding constants for phosphatidylserine and cardiolipin are about double those for phosphatidylglycerol. Binding to annular sites around the circumference of the KcsA tetramer are different on the extracellular and intracellular faces of the membrane. On the extracellular face of the membrane the binding constants for anionic lipids are similar to those for phosphatidylcholine, the lack of specificity being consistent with the lack of any marked clusters of charged residues on KcsA close to the membrane on the extracellular side. In contrast, binding to annular sites on the intracellular side of the membrane shows a distinct structural specificity, with binding of phosphatidic acid and phosphatidylglycerol being stronger than binding of phosphatidylcholine, whereas binding constants for phosphatidylserine and cardiolipin are similar to that for phosphatidylcholine. It is suggested that this pattern of binding follows from the pattern of charge distribution on KcsA on the intracellular side of the membrane. PMID:16199503

  8. The role of electrolyte anions (ClO{sub 4}{sup {minus}}, NO{sub 3}{sup {minus}}, and Cl{sup {minus}}) in divalent metal (M{sup 2+}) adsorption on oxide and hydroxide surfaces in salt solutions

    SciTech Connect

    Criscenti, L.J.; Sverjensky, D.A.

    1999-12-01

    Adsorption of divalent metal ions (M{sup 2+}) onto oxide and hydroxide surfaces from solutions of strong electrolytes has typically been inferred to take place without the involvement of the electrolyte anion. Only in situations where M{sup 2+} forms a strong enough aqueous complex with the electrolyte anion (for example, CdCl{sup +} or PbCl{sup +}) has it been frequently suggested that the metal and the electrolyte anion adsorb simultaneously. A review of experimental data for the adsorption of Cd{sup 2+}, Pb{sup 2+}, Co{sup 2+}, UO{sub 2}{sup 2+}, Zn{sup 2+}, Cu{sup 2+}, Ba{sup 2+}, Sr{sup 2+}, and Ca{sup 2+} onto quartz, silica, goethite, hydrous ferric oxide, corundum, {gamma}-alumina, anatase, birnessite, and magnetite, from NaNO{sub 3}, KNO{sub 3}, NaCl, and NaClO{sub 4} solutions over a wide range of ionic strengths (0.0001 M-1.0 M), reveals that transition and heavy metal adsorption behavior with ionic strength is a function of the type of electrolyte. In NaNO{sub 3} solutions, metal adsorption exhibits little or no dependence on the ionic strength of the solution. However, in NaCl solutions, transition and heavy metal adsorption decreases strongly with increasing ionic strength. In NaClO{sub 4} solutions, metal adsorption decreases strongly with increasing ionic strength. In NaClO{sub 4} solutions, metal adsorption exhibits little dependence on ionic strength but is often suggestive of an increase in metal adsorption with increasing ionic strength. Analysis of selected adsorption edges was carried out using the extended triple-layer model and aqueous speciation models that included metal-nitrate, metal-chloride, and metal-hydroxide complexes.

  9. Anion exchange membrane

    DOEpatents

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

    2013-05-07

    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  10. Aluminum Hydroxide

    MedlinePlus

    Aluminum hydroxide is used for the relief of heartburn, sour stomach, and peptic ulcer pain and to ... Aluminum hydroxide comes as a capsule, a tablet, and an oral liquid and suspension. The dose and ...

  11. Magnesium Hydroxide

    MedlinePlus

    Magnesium hydroxide is used on a short-term basis to treat constipation.This medication is sometimes prescribed ... Magnesium hydroxide come as a tablet and liquid to take by mouth. It usually is taken as ...

  12. Cu sbnd Al sbnd Fe layered double hydroxides with CO32- and anionic surfactants with different alkyl chains in the interlayer

    NASA Astrophysics Data System (ADS)

    Trujillano, Raquel; Holgado, María Jesús; González, José Luis; Rives, Vicente

    2005-08-01

    Layered double hydroxides (LDHs), with the hydrotalcite-like structure containing Cu(II), Al(III) and Fe(III) in the layers, and different alkyl sulfonates in the interlayer, have been prepared and characterized by powder X-ray diffraction, FT-IR spectroscopy, differential thermal analysis and thermogravimetric analysis. Pure crystalline phases have been obtained in all cases. Upon heating, combustion of the organic chain takes place at lower temperature than the corresponding sodium salts.

  13. Tens of micron-sized unilamellar nanosheets of Y/Eu layered rare-earth hydroxide: efficient exfoliation via fast anion exchange and their self-assembly into oriented oxide film with enhanced photoluminescence

    NASA Astrophysics Data System (ADS)

    Zhu, Qi; Li, Ji-Guang; Li, Xiaodong; Sun, Xudong; Qi, Yang; Zhu, Miaoyong; Sakka, Yoshio

    2014-02-01

    Layered rare-earth hydroxide (LRH) crystals of (Y0.95Eu0.05)2(OH)5NO3·nH2O with a lateral size of ˜ 300 μm and a thickness of ˜ 9 μm have been synthesized via a hydrothermal reaction of mixed nitrate solutions in the presence of mineralizer NH4NO3 at 200 °C for 24 h. LRH exhibits the ability to undergo intercalation and anion exchange with DS- (C12H25OSO3-) via hydrothermal treatment. Compared with traditional anion exchange at room temperature, hydrothermal processing not only shortens the anion exchange time from 720 to 24 h but also increases the basal spacing. The arrangements of DS- in the interlayer of LRH are significantly affected by the DS- concentration and reaction temperature, and the basal spacing of the LRH-DS sample in the crystal edge is assumed to be larger than that in the crystal center. A higher DS- concentration and reaction temperature both induce more intercalation of DS- anions into the interlayer gallery, thus yielding a larger basal spacing. Unilamellar nanosheets with a lateral size of ⩾60 μm and a thickness of ˜ 1.6 nm can be obtained by delaminating LRH-DS in formamide. The resultant unilamellar nanosheets are single crystalline. Transparent (Y0.95Eu0.05)2O3 phosphor films with a uniform [111] orientation and a layer thickness of ˜ 90 nm were constructed with the nanosheets as building blocks via spin-coating, followed by proper annealing. The oriented oxide film exhibits a strong red emission at 614 nm (the 5D0-7F2 transition of Eu3+), whose intensity is ˜ 2 times that of the powder form owing to the significant exposure of the (222) facets.

  14. Thermal aging of interfacial polymer chains in ethylene-propylene-diene terpolymer/aluminum hydroxide composites: solid-state NMR study.

    PubMed

    Gabrielle, Brice; Lorthioir, Cédric; Lauprêtre, Françoise

    2011-11-01

    The possible influence of micrometric-size filler particles on the thermo-oxidative degradation behavior of the polymer chains at polymer/filler interfaces is still an open question. In this study, a cross-linked ethylene-propylene-diene (EPDM) terpolymer filled by aluminum trihydrate (ATH) particles is investigated using (1)H solid-state NMR. The time evolution of the EPDM network microstructure under thermal aging at 80 °C is monitored as a function of the exposure time and compared to that of an unfilled EPDM network displaying a similar initial structure. While nearly no variations of the topology are observed on the neat EPDM network over 5 days at 80 °C, a significant amount of chain scission phenomena are evidenced in EPDM/ATH. A specific surface effect induced by ATH on the thermodegradative properties of the polymer chains located in their vicinity is thus pointed out. Close to the filler particles, a higher amount of chain scissions are detected, and the characteristic length scale related to these interfacial regions displaying a significant thermo-oxidation process is determined as a function of the aging time.

  15. NICKEL HYDROXIDES

    SciTech Connect

    MCBREEN,J.

    1997-11-01

    Nickel hydroxides have been used as the active material in the positive electrodes of several alkaline batteries for over a century. These materials continue to attract a lot of attention because of the commercial importance of nickel-cadmium and nickel-metal hydride batteries. This review gives a brief overview of the structure of nickel hydroxide battery electrodes and a more detailed review of the solid state chemistry and electrochemistry of the electrode materials. Emphasis is on work done since 1989.

  16. Effect of Molecular Architecture of PDMAEMA-POEGMA Random and Block Copolymers on Their Adsorption on Regenerated and Anionic Nanocelluloses and Evidence of Interfacial Water Expulsion.

    PubMed

    Vuoriluoto, Maija; Orelma, Hannes; Johansson, Leena-Sisko; Zhu, Baolei; Poutanen, Mikko; Walther, Andreas; Laine, Janne; Rojas, Orlando J

    2015-12-10

    Block copolymers of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) with varying block sizes were synthesized by consecutive reversible addition-fragmentation chain transfer (RAFT) polymerization and then exposed to cellulose substrates with different anionic charge density. The extent and dynamics of quaternized PDMAEMA-b-POEGMA adsorption on regenerated cellulose, cellulose nanofibrils (CNF), and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNF) was determined by using electromechanical and optical techniques, namely, quartz crystal microbalance (QCM-D) and surface plasmon resonance (SPR), respectively. PDMAEMA-b-POEGMA equilibrium adsorption increased with the anionic charge of cellulose, an indication of electrostatic interactions. Such an observation was further confirmed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Depending on their architecture, adsorption on TOCNF of some of the PDMAEMA-b-POEGMA copolymers produced a significant reduction in QCM frequency, as expected from large mass uptake, while surprisingly, other copolymers induced the opposite effect. This latter, remarkable behavior was ascribed to coupled water expulsion from the interface upon charge neutralization of anionic surface sites with adsorbing cationic polymer segments. These observations were further investigated with SPR and QCM-D measurements using deuterium oxide solvent exchange to determine the amount of coupled water at the TOCNF-block copolymer interface. Finally, random copolymers with similar composition adsorbed to a larger extent compared to the respective block copolymers, revealing the effect of adsorbed loops and tails as well as hydration.

  17. SEPARATION OF PLUTONIUM HYDROXIDE FROM BISMUTH HYDROXIDE

    DOEpatents

    Watt, G.W.

    1958-08-19

    An tmproved method is described for separating plutonium hydroxide from bismuth hydroxide. The end product of the bismuth phosphate processes for the separation amd concentration of plutonium is a inixture of bismuth hydroxide amd plutonium hydroxide. It has been found that these compounds can be advantageously separated by treatment with a reducing agent having a potential sufficient to reduce bismuth hydroxide to metalltc bisinuth but not sufficient to reduce the plutonium present. The resulting mixture of metallic bismuth and plutonium hydroxide can then be separated by treatment with a material which will dissolve plutonium hydroxide but not metallic bismuth. Sodiunn stannite is mentioned as a preferred reducing agent, and dilute nitric acid may be used as the separatory solvent.

  18. Calcium hydroxide poisoning

    MedlinePlus

    Hydrate - calcium; Lime milk; Slaked lime ... Calcium hydroxide ... These products contain calcium hydroxide: Cement Limewater Many industrial solvents and cleaners (hundreds to thousands of construction products, flooring strippers, brick cleaners, cement ...

  19. Praseodymium(III) sulfate hydroxide, Pr(SO(4))(OH).

    PubMed

    Wang, Xiao-Juan; Cheng, Jian-Wen

    2011-01-15

    The title compound, Pr(SO(4))(OH), obtained under hydro-thermal conditions, consists of Pr(III) ions coordinated by nine O atoms from six sulfate groups and three hydroxide anions. The bridging mode of the O atoms results in the formation of a three-dimensional framework, stabilized by two O-H⋯O hydrogen-bonding inter-actions.

  20. Effect of poly(vinyl alcohol-co-vinyl acetate) copolymer blockiness on the dynamic interfacial tension and dilational viscoelasticity of polymer-anionic surfactant complex at the water-1-chlorobutane interface.

    PubMed

    Atanase, Leonard Ionut; Bistac, Sophie; Riess, Gérard

    2015-04-01

    Poly(vinyl alcohol-co-vinyl acetate) (PVA) copolymers obtained by partial hydrolysis of poly(vinyl acetate) (PVAc) are of practical importance for many applications, including emulsion and suspension polymerization processes. Their molecular characteristics have a major influence on the colloidal and interfacial properties. The most significant characteristics are represented by the average degree of hydrolysis D̅H̅, average degree of polymerization D̅P̅w̅ but also by the average acetate sequence length n(VAc)(0) which designates the so-called blockiness. Colloidal aggregates were observed in the aqueous PVA solutions having a D̅H̅ value of 73 mol%. The volume fraction of these aggregates at a given D̅H̅ value is directly correlated to the blockiness. Three PVA samples with identical D̅H̅ and D̅P̅w̅ but different blockiness were examined. By pendant drop and oscillating pendant drop techniques it was shown that the PVA sample having the lowest blockiness and thus the lowest volume fraction of colloidal aggregates has lower interfacial tension and elastic modulus E' values. On the contrary, the corresponding values are highest for PVA sample of higher blockiness. In the presence of sodium dodecyl sulfate (SDS), the colloidal aggregates are disaggregated by complex formation due to the hydrophobic-hydrophobic interactions. The PVA-SDS complex acts as a partial polyelectrolyte that induces the stretching of the chains and thus a reduction of the interface thickness. In this case, the interfacial tension and the elastic modulus both increase with increasing SDS concentration for all three PVA samples and the most significant effect was noticed for the most "blocky" copolymer sample.

  1. Self-Doping, O2-Stable, n-Type Interfacial Layer for Organic Electronics

    SciTech Connect

    Reilly, T. H. III; Hains, A. W.; Chen, H. Y.; Gregg, B. A.

    2012-04-01

    Solid films of a water-soluble dicationic perylene diimide salt, perylene bis(2-ethyltrimethylammonium hydroxide imide), Petma{sup +}OH{sup -}, are strongly doped n-type by dehydration and reversibly de-doped by hydration. The hydrated films consist almost entirely of the neutral perylene diimide, PDI, while the dehydrated films contain {approx}50% PDI anions. The conductivity increases by five orders of magnitude upon dehydration, probably limited by film roughness, while the work function decreases by 0.74 V, consistent with an n-type doping density increase of {approx}12 orders of magnitude. Remarkably, the PDI anions are stable in dry air up to 120 C. The work function of the doped film, {phi} (3.96 V vs. vacuum), is unusually negative for an O{sub 2}-stable contact. Petma{sup +} OH{sup -} is also characterized as an interfacial layer, IFL, in two different types of organic photovoltaic cells. Results are comparable to state of the art cesium carbonate IFLs, but may improve if film morphology can be better controlled. The films are stable and reversible over many months in air and light. The mechanism of this unusual self-doping process may involve the change in relative potentials of the ions in the film caused by their deshielding and compaction as water is removed, leading to charge transfer when dry.

  2. Potassium hydroxide poisoning

    MedlinePlus

    This article discusses poisoning from swallowing or touching potassium hydroxide or products that contain this chemical. This article is for information only. Do NOT use it to treat or manage an actual poison exposure. If ...

  3. Interfacial tension in immiscible mixtures of alkali halides.

    PubMed

    Lockett, Vera; Rukavishnikova, Irina V; Stepanov, Victor P; Tkachev, Nikolai K

    2010-02-01

    The interfacial tension of the liquid-phase interface in seven immiscible reciprocal ternary mixtures of lithium fluoride with the following alkali halides: CsCl, KBr, RbBr, CsBr, KI, RbI, and CsI was measured using the cylinder weighing method over a wide temperature range. It was shown that for all mixtures the interfacial tension gradually decreases with growing temperature. The interfacial tension of the reciprocal ternary mixtures at a given temperature increases both with the alkali cation radius (K(+) < Rb(+) < Cs(+)) and with the radius of the halogen anion (Cl(-) < Br(-) < I(-)). PMID:20094678

  4. Hydroxide-catalyzed bonding

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung (Inventor)

    2003-01-01

    A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

  5. Part I. Layered Double Hydroxides

    NASA Astrophysics Data System (ADS)

    Dimotakis, Emmanuel Dimitrios

    A new general method for the preparation of well -ordered layered double hydroxides (LDHs), (Mg_ {rm 1-x}Al_{ rm x} (OH)_2) (X^{rm n-}) _{rm n/x}{cdot}yH _2O, interlayered by organic anions has been developed. It is based on the reaction of meixnerite, (Mg_3Al(OH)_8) (OH) cdot2H_2O, with the free acid form of the desired anion--using glycerol as a swelling agent--to yield single crystalline products that are not readily available by conventional synthetic methods. The (Mg_3Al(OH) _8) -adipate and -p-toluenesulfonate derivatives undergo facile ion exchange reactions with Keggin-type (XM_{12}O_ {40}) ^{rm n -} or lacunary (XM_{11 }O_{39}) ^{rm m-} polyoxometalates (POMs) to form well-ordered, microporous pillared derivatives with the highest N_2 BET surface areas reported to date, namely 107 and 155 m^2 /g, respectively. Meixnerite, (Mg_3Al(OH) _8) (OH) cdot2H _2O, has unexpectedly been found to undergo similar ion exchange reactions, in a topotactic way, with retention of the structure of the intercalated POMs. The meixnerite was conveniently prepared for the first time from calcination of (Mg_3Al(OH) _8) (CO_3) _{0.5}{cdot}2H _2O and aqueous hydrolysis of the resulting NaCl-type solid solution. Metal carbonyl clusters have also been examined for ion-exchange (i.e., { (Pt _3(CO)_6) _{rm n}}^ {2-}) in these LDH-precursors. This chemistry is compared with the surface chemistry of (Mg_3 Al(OH)_8) (X^ {rm n-}) _{ rm 1/n}{cdot}2H _2O (X = CO_3^{2 -} or OH^{-}). It has been shown that the surface hydrolysis reaction: CO _3^{2-} + H _2O longrightarrow HCO_3^{-} + OH ^-, causes reductive condensation reactions of neutral carbonyl clusters with the LDH. The reactions were as efficient as with Na metal in solution. In part II of this work, Li-fluorohectorite, has been pillared with titanium polyoxocations derived from the acidic hydrolysis of TiCl_4 or Ti(i-OC_3H_7) _4. Raman spectroscopy of the product indicates that the pillars have a structure analogous to TiO_2(B) phase

  6. Interfacial activity in alkaline flooding enhanced oil recovery

    SciTech Connect

    Chan, M.K.

    1981-01-01

    The ionization of long-chained organic acids in the crude oil to form soaps was shown to be primarily responsible for the lowering of oil-water interfacial tension at alkaline pH. These active acids can be concentrated by silica gel chromatography into a minor polar fraction. An equilibrium chemical model was proposed based on 2 competing reactions: the ionization of acids to form active anions, and the formation of undissociated soap between acid anions and sodium ions. It correlates the interfacial activity with the interfacial concentration of active acid anions which is expressed in terms of the concentrations of the chemical species in the system. The model successfully predicts the observed oil-alkaline solution interfacial phenomenon, including its dependence on pH, alkali and salt concentrations, type of acid present and type of soap formed. Flooding at different alkali concentrations to activate different acid species present in the crude was shown to give better recovery than flooding at a single high alkali concentration. Treating the crude oil with a dilute solution of mineral acids liberates additional free active acids and yields better interfacial activity during subsequent alkali contact.

  7. Nickel hydroxide electrode. 3: Thermogravimetric investigations of nickel (II) hydroxides

    NASA Technical Reports Server (NTRS)

    Dennstedt, W.; Loeser, W.

    1982-01-01

    Water contained in Ni hydroxide influences its electrochemical reactivity. The water content of alpha and beta Ni hydroxides is different with respect to the amount and bond strength. Thermogravimetric experiments show that the water of the beta Ni hydroxides exceeding the stoichiometric composition is completely removed at 160 deg. The water contained in the interlayers of the beta hydroxide, however, is removed only at higher temperatures, together with the water originating from the decomposition of the hydroxide. These differences are attributed to the formation of II bonds within the interlayers and between interlayers and adjacent main layers. An attempt is made to explain the relations between water content and the oxidizability of the Ni hydroxides.

  8. Highly Water Resistant Anion Exchange Membrane for Fuel Cells.

    PubMed

    Yang, Zhengjin; Hou, Jianqiu; Wang, Xinyu; Wu, Liang; Xu, Tongwen

    2015-07-01

    For anion exchange membranes (AEMs), achieving efficient hydroxide conductivity without excessive hydrophilicity presents a challenge. Hence, new strategies for constructing mechanically strengthened and hydroxide conductive (especially at controlled humidity) membranes are critical for developing better AEMs. Macromolecular modification involving ylide chemistry (Wittig reaction) for the fabrication of novel AEMs with an interpenetrating polymer network structure is reported. The macromolecular modification is cost effective, facile, and based on a one-pot synthesis. AEM water uptake is reduced to 3.6 wt% and a high hydroxide conductivity (69.7 mS cm(-1) , 90 °C) is achieved simultaneously. More importantly, the membrane exhibits similar tensile strength (>35 MPa) and comparable flexibility in both dry and wet states. These AEMs could find further applications within anion exchange membrane fuel cells with low humidity or photoelectric assemblies.

  9. Highly Water Resistant Anion Exchange Membrane for Fuel Cells.

    PubMed

    Yang, Zhengjin; Hou, Jianqiu; Wang, Xinyu; Wu, Liang; Xu, Tongwen

    2015-07-01

    For anion exchange membranes (AEMs), achieving efficient hydroxide conductivity without excessive hydrophilicity presents a challenge. Hence, new strategies for constructing mechanically strengthened and hydroxide conductive (especially at controlled humidity) membranes are critical for developing better AEMs. Macromolecular modification involving ylide chemistry (Wittig reaction) for the fabrication of novel AEMs with an interpenetrating polymer network structure is reported. The macromolecular modification is cost effective, facile, and based on a one-pot synthesis. AEM water uptake is reduced to 3.6 wt% and a high hydroxide conductivity (69.7 mS cm(-1) , 90 °C) is achieved simultaneously. More importantly, the membrane exhibits similar tensile strength (>35 MPa) and comparable flexibility in both dry and wet states. These AEMs could find further applications within anion exchange membrane fuel cells with low humidity or photoelectric assemblies. PMID:25962480

  10. The effect of aluminum hydroxide dissolution on the bleeding of aluminum lake dyes.

    PubMed

    Desai, A; Peck, G E; Lovell, J E; White, J L; Hem, S L

    1993-10-01

    The effect of pH on the bleeding of FD&C yellow No. 5 aluminum lake and FD&C red No. 40 aluminum lake was investigated. The pH-bleeding profiles corresponded to the pH-solubility profile of aluminum hydroxide. The similarity of the bleeding profiles of both lake dyes and the pH-solubility profile of aluminum hydroxide indicates that pH related bleeding, other than that occurring by competition with anions, is a result of dissolution of the aluminum hydroxide substrate. This dissolution is related to the properties of the substrate rather than to the structure of adsorbed dye.

  11. Device to generate high purity hydroxide solution in-line for ion chromatography.

    PubMed

    Masunaga, Hiroto; Higo, Yuji; Ishii, Mizuo; Maruyama, Noboru; Yamazaki, Shigeo

    2016-05-01

    Herein, we report a new device that generates a high-purity hydroxide solution in line. The device's container has three compartments that are isolated from each other by two cation exchange (CE) membranes. In each end of the container, an electrode is installed. The three compartments are filled with ion exchange resins. A bipolar boundary is a composite boundary comprising anion- and cation-exchangers. This device has two bipolar boundaries, which are used to separate the location of hydroxide solution generation from the location where water is electrolyzed. Therefore, it can produce high-purity hydroxide solutions that are free from gases and anionic impurities. The hydroxide solution is generated on the basis of an electrokinetic phenomenon at the surfaces of ion-exchange resins and membranes in an electric field; NaOH concentration can be controlled at rates from 0.01 to 100mM per 1mL/min by adjusting the electrical current (0-200mA) applied to the device. As the generated solution is used as an eluent for a suppressed anion chromatography, the electrical conductivity of the effluent from the suppressor is as low as that of ultra-pure water. Thus, the noise of the base-line electrical conductivity is improved, and so the detection limit of anions on the sub-ng/mL order can be achieved.

  12. Device to generate high purity hydroxide solution in-line for ion chromatography.

    PubMed

    Masunaga, Hiroto; Higo, Yuji; Ishii, Mizuo; Maruyama, Noboru; Yamazaki, Shigeo

    2016-05-01

    Herein, we report a new device that generates a high-purity hydroxide solution in line. The device's container has three compartments that are isolated from each other by two cation exchange (CE) membranes. In each end of the container, an electrode is installed. The three compartments are filled with ion exchange resins. A bipolar boundary is a composite boundary comprising anion- and cation-exchangers. This device has two bipolar boundaries, which are used to separate the location of hydroxide solution generation from the location where water is electrolyzed. Therefore, it can produce high-purity hydroxide solutions that are free from gases and anionic impurities. The hydroxide solution is generated on the basis of an electrokinetic phenomenon at the surfaces of ion-exchange resins and membranes in an electric field; NaOH concentration can be controlled at rates from 0.01 to 100mM per 1mL/min by adjusting the electrical current (0-200mA) applied to the device. As the generated solution is used as an eluent for a suppressed anion chromatography, the electrical conductivity of the effluent from the suppressor is as low as that of ultra-pure water. Thus, the noise of the base-line electrical conductivity is improved, and so the detection limit of anions on the sub-ng/mL order can be achieved. PMID:27063368

  13. Electroosmotic Flow Hysteresis for Dissimilar Anionic Solutions.

    PubMed

    Lim, An Eng; Lim, Chun Yee; Lam, Yee Cheong

    2016-08-16

    Electroosmotic flow (EOF) with two or more fluids is often encountered in various microfluidic applications. However, no investigation has hitherto been conducted to investigate the hysteretic or flow direction-dependent behavior during displacement flow of solutions with dissimilar anion species. In this investigation, EOF of dissimilar anionic solutions was studied experimentally through the current monitoring method and numerically through finite element simulations. As opposed to other conventional displacement flows, EOF involving dissimilar anionic solutions exhibits counterintuitive behavior, whereby the current-time curve does not reach the steady-state value of the displacing electrolyte. Two distinct mechanics have been identified as the causes for this observation: (a) ion concentration adjustment when the displacing anions migrate upstream against EOF due to competition between the gradients of electromigrative and convective fluxes and (b) ion concentration readjustment induced by the static diffusive interfacial region between the dissimilar fluids which can only be propagated throughout the entire microchannel with the presence of EOF. The resultant ion distributions lead to the flow rate to be directional-dependent, indicating that the flow conditions are asymmetric between these two different flow directions. The outcomes of this investigation contribute to the in-depth understanding of flow behavior in microfluidic systems involving inhomogeneous fluids, particularly dissimilar anionic solutions. The understanding of EOF hysteresis is fundamentally important for the accurate prediction of analytes transport in microfluidic devices under EOF. PMID:27426052

  14. One-dimensional copper hydroxide nitrate nanorods and nanobelts for radiochemical applications.

    PubMed

    Liu, Bin

    2012-11-21

    I report a facile wet-chemical method for the synthesis of one-dimensional copper hydroxide nitrate nanostructures in 2-propanol under solvothermal conditions. Single-crystalline nearly monodispersed copper hydroxide nitrate nanorods and nanobelts with selected breadths in the range of 100 nm to 1 μm have been successfully prepared by a solvothermal method through controlling the experimental parameters, including initial concentrations of reagents, reaction temperature, solvent and reaction time. The resultant nanorods and nanobelts were characterized using FESEM, TEM, XRD, FTIR and TGA techniques. Upon thermal calcination, the copper hydroxide nitrate nanorods and nanobelts self-assemble into one-dimensional arrays (rods, belts or tubes) of copper oxide nanoparticles. The as-prepared copper hydroxide nitrate nanorods and nanobelts were tested as ion exchangers for removal of long-lived radioactive anions such as (129)I(-) and (99)TcO(4)(-). The copper hydroxide nitrate nanorods or nanobelts were over two times more active in the removal of anion species than copper hydroxide nitrate nanoplatelets. PMID:23070067

  15. Removal of boron species by layered double hydroxides: a review.

    PubMed

    Theiss, Frederick L; Ayoko, Godwin A; Frost, Ray L

    2013-07-15

    Boron, which is an essential element for plants, is toxic to humans and animals at high concentrations. Layered double hydroxides (LDHs) and thermally activated LDHs have shown good uptake of a range of boron species in laboratory scale experiments when compared to current available methods, which are for the most part ineffective or prohibitively expensive. LDHs were able to remove anions from water by anion exchange, the reformation (or memory) effect and direct precipitation. The main mechanism of boron uptake appeared to be anion exchange, which was confirmed by powder X-ray diffraction (XRD) measurements. Solution pH appeared to have little effect on boron sorption while thermal activation did not always significantly improve boron uptake. In addition, perpetration of numerous LDHs with varying boron anions in the interlayer region by direct co-precipitation and anion exchange have been reported by a number of groups. The composition and orientation of the interlayer boron ions could be identified with reasonable certainty by applying a number of characterisation techniques including: powder XRD, nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. There is still considerable scope for future research on the application of LDHs for the removal of boron contaminants.

  16. Layered-double-hydroxide-modified electrodes: electroanalytical applications.

    PubMed

    Tonelli, Domenica; Scavetta, Erika; Giorgetti, Marco

    2013-01-01

    Two-dimensional inorganic solids, such as layered double hydroxides (LDHs), also defined as anionic clays, have open structures and unique anion-exchange properties which make them very appropriate materials for the immobilization of anions and biomolecules that often bear an overall negative charge. This review aims to describe the important aspects and new developments of electrochemical sensors and biosensors based on LDHs, evidencing the research from our own laboratory and other groups. It is intended to provide an overview of the various types of chemically modified electrodes that have been developed with these 2D layered materials, along with the significant advances made over the last several years. In particular, we report the main methods used for the deposition of LDH films on different substrates, the conductive properties of these materials, the possibility to use them in the development of membranes for potentiometric anion analysis, the early analytical applications of chemically modified electrodes based on the ability of LDHs to preconcentrate redox-active anions and finally the most recent applications exploiting their electrocatalytic properties. Another promising application field of LDHs, when they are employed as host structures for enzymes, is biosensing, which is described considering glucose as an example.

  17. Removal of boron species by layered double hydroxides: a review.

    PubMed

    Theiss, Frederick L; Ayoko, Godwin A; Frost, Ray L

    2013-07-15

    Boron, which is an essential element for plants, is toxic to humans and animals at high concentrations. Layered double hydroxides (LDHs) and thermally activated LDHs have shown good uptake of a range of boron species in laboratory scale experiments when compared to current available methods, which are for the most part ineffective or prohibitively expensive. LDHs were able to remove anions from water by anion exchange, the reformation (or memory) effect and direct precipitation. The main mechanism of boron uptake appeared to be anion exchange, which was confirmed by powder X-ray diffraction (XRD) measurements. Solution pH appeared to have little effect on boron sorption while thermal activation did not always significantly improve boron uptake. In addition, perpetration of numerous LDHs with varying boron anions in the interlayer region by direct co-precipitation and anion exchange have been reported by a number of groups. The composition and orientation of the interlayer boron ions could be identified with reasonable certainty by applying a number of characterisation techniques including: powder XRD, nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. There is still considerable scope for future research on the application of LDHs for the removal of boron contaminants. PMID:23635479

  18. Structural features of intercalated CaFe-layered double hydroxides studied by X-ray diffractometry, infrared spectroscopy and computations

    NASA Astrophysics Data System (ADS)

    Ferencz, Zs.; Ádok-Sipiczki, M.; Hannus, I.; Sipos, P.; Pálinkó, I.

    2015-06-01

    The intercalation of various N-containing carboxylic acid anions into CaFe-layered double hydroxides was performed by the dehydration-rehydration method. Particular attention was paid to the effect of solvent mixture used during preparation. It was found that various solvent mixtures resulted in different interlayer distances and, thus, different arrangements of the anions between the layers. The dimensions of the intercalated anions and detailed analysis of the infrared spectra gave clues for the reasonable prediction of the spatial arrangements of the anions in the interlamellar space.

  19. 21 CFR 184.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Potassium hydroxide. 184.1631 Section 184.1631... Listing of Specific Substances Affirmed as GRAS § 184.1631 Potassium hydroxide. (a) Potassium hydroxide..., including pellets, flakes, sticks, lumps, and powders. Potassium hydroxide is obtained commercially from...

  20. 21 CFR 184.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Potassium hydroxide. 184.1631 Section 184.1631... Listing of Specific Substances Affirmed as GRAS § 184.1631 Potassium hydroxide. (a) Potassium hydroxide..., including pellets, flakes, sticks, lumps, and powders. Potassium hydroxide is obtained commercially from...

  1. 21 CFR 184.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Potassium hydroxide. 184.1631 Section 184.1631... Listing of Specific Substances Affirmed as GRAS § 184.1631 Potassium hydroxide. (a) Potassium hydroxide..., including pellets, flakes, sticks, lumps, and powders. Potassium hydroxide is obtained commercially from...

  2. 21 CFR 184.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Potassium hydroxide. 184.1631 Section 184.1631 Food... Specific Substances Affirmed as GRAS § 184.1631 Potassium hydroxide. (a) Potassium hydroxide (KOH, CAS Reg... pellets, flakes, sticks, lumps, and powders. Potassium hydroxide is obtained commercially from...

  3. Formation of Cr(III) hydroxides from chrome alum solutions. 1: Precipitation of active chromium hydroxide

    SciTech Connect

    Avena, M.J.; Giacomelli, C.E.; De Pauli, C.P.

    1996-06-25

    The hydrolysis of Cr(III) and precipitation of colloidal chromium hydroxides are important processes occurring in soils and natural waters. The formation of active chromium hydroxide, Cr(OH){sub 3}{center_dot}3H{sub 2}O, was studied through potentiometric titrations and turbidimetric measurements. UV-Vis and IR spectroscopies were also employed to characterize the synthesized solid. The rapid addition of NaOH solution to aqueous chrome alum (KCr(SO{sub 4}){sub 2}{center_dot}12H{sub 2}O) solutions caused the immediate precipitation of the active material. Only monomeric Cr(III) species seemed to be participating in the precipitation process; neither chromium polymers nor complexes with anions (SO{sub 4}{sup 2{minus}}, Cl{sup {minus}}, NO{sub 3}{sup {minus}}, ClO{sub 4}{sup {minus}}) influenced the fast formation of Cr(OH){sub 3}{center_dot}3H{sub 2}O. Titration studies allowed the determination of several hydrolysis and precipitation constants for Cr(III). Nevertheless, they cannot be used for the estimate of Cr(OH){sub 3}{sup 0} formation constant.

  4. Emulsions for interfacial filtration.

    SciTech Connect

    Grillet, Anne Mary; Bourdon, Christopher Jay; Souza, Caroline Ann; Welk, Margaret Ellen; Hartenberger, Joel David; Brooks, Carlton, F.

    2006-11-01

    We have investigated a novel emulsion interfacial filter that is applicable for a wide range of materials, from nano-particles to cells and bacteria. This technology uses the interface between the two immiscible phases as the active surface area for adsorption of targeted materials. We showed that emulsion interfaces can effectively collect and trap materials from aqueous solution. We tested two aqueous systems, a bovine serum albumin (BSA) solution and coal bed methane produced water (CBMPW). Using a pendant drop technique to monitor the interfacial tension, we demonstrated that materials in both samples were adsorbed to the liquid-liquid interface, and did not readily desorb. A prototype system was built to test the emulsion interfacial filter concept. For the BSA system, a protein assay showed a progressive decrease in the residual BSA concentration as the sample was processed. Based on the initial prototype operation, we propose an improved system design.

  5. Advancements in Anion Exchange Membrane Cations

    SciTech Connect

    Sturgeon, Matthew R.; Long, Hai; Park, Andrew M.; Pivovar, Bryan S.

    2015-10-15

    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  6. Synthesis, characterization, and controlled release antibacterial behavior of antibiotic intercalated Mg–Al layered double hydroxides

    SciTech Connect

    Wang, Yi; Zhang, Dun

    2012-11-15

    Graphical abstract: The antibiotic anion released from Mg–Al LDHs provides a controlled release antibacterial activity against the growth of Micrococcus lysodeikticus in 3.5% NaCl solution. Highlights: ► Antibiotic anion intercalated LDHs were synthesized and characterized. ► The ion-exchange one is responsible for the release process. ► The diffusion through particle is the release rate limiting step. ► LDHs loaded with antibiotic anion have high antibacterial capabilities. -- Abstract: Antibiotic–inorganic clay composites including four antibiotic anions, namely, benzoate (BZ), succinate (SU), benzylpenicillin (BP), and ticarcillin (TC) anions, intercalated Mg–Al layered double hydroxides (LDHs) were synthesized via ion-exchange. Powder X-ray diffraction and Fourier transform infrared spectrum analyses showed the successful intercalation of antibiotic anion into the LDH interlayer. BZ and BP anions were accommodated in the interlayer region as a bilayer, whereas SU and TC anions were intercalated in a monolayer arrangement. Kinetic simulation of the release data indicated that ion-exchange was responsible for the release process, and the diffusion through the particles was the rate-limiting step. The antibacterial capabilities of LDHs loaded with antibiotic anion toward Micrococcus lysodeikticus growth were analyzed using a turbidimetric method. Significant high inhibition rate was observed when LDH nanohybrid was introduced in 3.5% NaCl solution. Therefore, this hybrid material may be applied as nanocontainer in active antifouling coating for marine equipment.

  7. Universal nanopatternable interfacial bonding.

    PubMed

    Ding, Yuzhe; Garland, Shaun; Howland, Michael; Revzin, Alexander; Pan, Tingrui

    2011-12-01

    A nanopatternable polydimethylsiloxane (PDMS) oligomer layer is demonstrated as an interfacial adhesive for its intrinsic transferability and universal adhesiveness. Utilizing the well-established surface modification and bonding techniques of PDMS surfaces, irreversible bonding is formed (up to 400 kPa) between a wide range of substrate pairs, representing ones within and across different materials categories, including metals, ceramics, thermoset, and thermoplastic polymers.

  8. The production and properties of gel precipitated aluminium hydroxide spheres containing imipramine.

    PubMed

    Ramsey, M P; Shaw, G G; Newton, J M; Lane, E S; Sammon, D C

    1984-01-01

    The production of aluminium hydroxide spheres containing imipramine by gel precipitation of liquid feed solutions has been described. Washing and heating procedures applied to the precipitated spheres markedly affected the rate of drug release from the spheres into 0.1M hydrochloric acid. Increasing the imipramine content of the spheres also altered the drug release rate. The effects described have been explained with reference to model theories of the precipitation and ageing of aluminium hydroxide gels in the presence and absence of 'foreign' anions.

  9. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

    SciTech Connect

    Soniat, Marielle; Rick, Steven W.; Kumar, Revati

    2015-07-28

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.

  10. Anion solvation in alcohols

    SciTech Connect

    Jonah, C.D.; Xujia, Zhang; Lin, Yi

    1996-03-01

    Anion solvation is measured in alcohols using pump-probe pulse radiolysis and the activation energy of solvation is determined. Solvation of an anion appears to be different than excited state solvation. The continuum dielectric model does not appear to explain the results.

  11. Adsorption kinetic and thermodynamic studies of phosphate onto tantalum hydroxide.

    PubMed

    Yu, Shi-Hua; Dong, Xiao-Le; Gong, Hong; Jiang, Heng; Liu, Zhi-Gang

    2012-12-01

    Tantalum hydroxide exhibits the ability for the removal of phosphate from aqueous solution. The kinetic study, adsorption isotherm, thermodynamic study, desorption, and foreign anions effect were examined in batch experiments. The kinetic process was very well described by a pseudo-second-order rate model. The adsorption isotherms showed that phosphate uptake fitted with a Langmuir-type model very well, with an increase of PO4(3-) adsorption capacity from 78.5 to 97.0 mg/g when the temperature increased from 298 to 338 K. The negative values of deltaG(0) and the positive values of deltaH(0) indicated that the phosphate adsorption process was spontaneous and endothermic naturally. While the deltaS(0) values obtained were positive, indicating an increase in randomness at the solid-liquid interface during the adsorption. Foreign anions tests showed that the presence of competitive ions cause minimal interference with the adsorption of phosphate on tantalum hydroxide.

  12. Hydroxide Degradation Pathways for Substituted Trimethylammonium Cations: A DFT Study

    SciTech Connect

    Long, H.; Kim, K.; Pivovar, B. S.

    2012-05-03

    Substituted trimethylammonium cations serve as small molecule analogues for tetherable cations in anion exchange membranes. In turn, these membranes serve as the basis for alkaline membrane fuel cells by allowing facile conduction of hydroxide. As these cations are susceptible to hydroxide attack, they degrade over time and greatly limit the lifetime of the fuel cell. In this research, we performed density functional theory calculations to investigate the degradation pathways of substituted trimethylammonium cations to probe the relative durability of cation tethering strategies in alkyl and aromatic tethers. Our results show that significant changes in calculated energy barriers occur when substitution groups change. Specifically, we have found that, when available, the Hofmann elimination pathway is the most vulnerable pathway for degradation; however, this barrier is also found to depend on the carbon chain length and number of hydrogens susceptible to Hofmann elimination. S{sub N}2 barriers were also investigated for both methyl groups and substitution groups. The reported findings give important insight into potential tethering strategies for trimethylammonium cations in anion exchange membranes.

  13. Hydroxide Degradation Pathways for Imidazolium Cations. A DFT Study

    SciTech Connect

    Long, H.; Pivovar, B.

    2014-05-15

    Imidazolium cations are promising candidates as covalently tetherable cations for application in anion exchange membranes. They have generated specific interest in alkaline membrane fuel cell applications where ammonium-based cations have been the most commonly applied but have been found to be susceptible to hydroxide attack. In the search for high stability cations, a detailed understanding of the degradation pathways and reaction barriers is required. In this work, we investigate imidazolium and benzimidazolium cations in the presence of hydroxide using density functional theory calculations for their potential in alkaline membrane fuel cells. Moreover, the dominant degradation pathway for these cations is predicted to be the nucleophilic addition–elimination pathway at the C-2 atom position on the imidazolium ring. Steric interferences, introduced by substitutions at the C-2, C-4, and C-5 atom positions, were investigated and found to have a significant, positive impact on calculated degradation energy barriers. Benzimidazolium cations, with their larger conjugated systems, are predicted to degrade much faster than their imidazolium counterparts. Our results provide important insight into designing stable cations for anion exchange membranes. Some of the molecules studied have significantly increased degradation energy barriers suggesting that they could possess significantly improved (several orders of magnitude) durability compared to traditional cations and potentially enable new applications.

  14. 21 CFR 582.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Additives § 582.1139 Ammonium hydroxide. (a) Product. Ammonium hydroxide. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or...

  15. 21 CFR 582.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Additives § 582.1139 Ammonium hydroxide. (a) Product. Ammonium hydroxide. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or...

  16. 21 CFR 184.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... Specific Substances Affirmed as GRAS § 184.1205 Calcium hydroxide. (a) Calcium hydroxide (Ca(OH)2, CAS Reg... lime. (b) The ingredient meets the specifications of the Food Chemicals Codex, 3d Ed. (1981), p....

  17. 21 CFR 184.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Specific Substances Affirmed as GRAS § 184.1205 Calcium hydroxide. (a) Calcium hydroxide (Ca(OH)2, CAS Reg... lime. (b) The ingredient meets the specifications of the Food Chemicals Codex, 3d Ed. (1981), p....

  18. 21 CFR 184.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... GRAS § 184.1205 Calcium hydroxide. (a) Calcium hydroxide (Ca(OH)2, CAS Reg. No. 1305-62-0) is also... meets the specifications of the Food Chemicals Codex, 3d Ed. (1981), p. 52, which is incorporated...

  19. 21 CFR 184.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Specific Substances Affirmed as GRAS § 184.1205 Calcium hydroxide. (a) Calcium hydroxide (Ca(OH)2, CAS Reg... lime. (b) The ingredient meets the specifications of the Food Chemicals Codex, 3d Ed. (1981), p....

  20. 21 CFR 184.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... Specific Substances Affirmed as GRAS § 184.1205 Calcium hydroxide. (a) Calcium hydroxide (Ca(OH)2, CAS Reg... lime. (b) The ingredient meets the specifications of the Food Chemicals Codex, 3d Ed. (1981), p....

  1. Layered double hydroxide formation in Bayer liquor and its promotional effect on oxalate precipitation

    SciTech Connect

    Perrotta, A.J.; Williams, F.

    1996-10-01

    Enhancing the precipitation of sodium oxalate from Bayer process liquor to improve the quality of alumina product remains an important objective for Bayer refining. The formation of layered double hydroxides by the reaction of alkaline earth oxides, such as lime and magnesia, with Bayer liquor gives a crystal structure which is capable of intercalating anions, both inorganic and organic, within its structure. Both lime and magnesia, with long contact times in Bayer liquor, show layered double hydroxide formation. This layered double hydroxide formation is accompanied with a decrease in the sodium oxalate content in the liquor from about 3 g/L to below 1 g/L. Short contact times lead to a destabilization of the liquor which facilitates sodium oxalate precipitation. Additional work on magnesium hydroxide shows, in comparison to lime and magnesia, much less layered double hydroxide formation with equivalent residence time in the liquor. Destabilization of the liquor also occurs, giving enhanced oxalate precipitation with less alumina being consumed in agreement with lower layered double hydroxide formation. Thermal regeneration of these structures, followed by in-situ recrystallization in Bayer liquor, also gives enhanced oxalate precipitation, suggesting that there is an opportunity for a regenerable oxalate reduction system. The implementation of these experiments and other related technology into the plant has resulted in the Purox Process for enhancing the precipitation of sodium oxalate from Bayer liquor.

  2. A study of the electrochemistry of nickel hydroxide electrodes with various additives

    NASA Astrophysics Data System (ADS)

    Zhu, Wen-Hua; Ke, Jia-Jun; Yu, Hong-Mei; Zhang, Deng-Jun

    Nickel composite electrodes (NCE) with various additives are prepared by a chemical impregnation method from nitrate solutions on sintered porous plaques. The electrochemical properties, such as utilization of active material, swelling and the discharge potential of the nickel oxide electrode (NOE) are determined mainly through the composition of the active material and the characteristics of nickel plaques. Most additives (Mg, Ca, Sr, Ba, Zn, Cd, Co, Li and Al hydroxide) exert effects on the discharge potential and swelling of the NOE. Chemical co-precipitation with the addition of calcium, zinc, magnesium and barium hydroxide increases the discharge potential by more than 20 mV, but that with zinc hydroxide results in an obvious decrease of active-material utilization and that with calcium and magnesium hydroxide produces a larger increase of electrode thickness. The effects of anion additives are also examined. Less than 1% mol of NiS in the active material increases the discharge potential. Cadmium, cobalt and zinc hydroxide are excellent additives for preventing swelling of the NCE. Slow voltammetry (0.2 mV s -1) in 6 M KOH is applied to characterize the oxygen-evolving potential of the NCE. The difference between the oxygen-evolution potential and the potential of the oxidation peak for the NCE with additives of calcium, lithium, barium and aluminium hydroxide is at least + 60 mV.

  3. Iridium Interfacial Stack (IRIS)

    NASA Technical Reports Server (NTRS)

    Spry, David James (Inventor)

    2015-01-01

    An iridium interfacial stack ("IrIS") and a method for producing the same are provided. The IrIS may include ordered layers of TaSi.sub.2, platinum, iridium, and platinum, and may be placed on top of a titanium layer and a silicon carbide layer. The IrIS may prevent, reduce, or mitigate against diffusion of elements such as oxygen, platinum, and gold through at least some of its layers.

  4. 21 CFR 582.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Potassium hydroxide. 582.1631 Section 582.1631 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1631 Potassium hydroxide. (a) Product. Potassium hydroxide. (b) Conditions of use....

  5. 21 CFR 582.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Potassium hydroxide. 582.1631 Section 582.1631 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1631 Potassium hydroxide. (a) Product. Potassium hydroxide. (b) Conditions of use....

  6. 21 CFR 582.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Potassium hydroxide. 582.1631 Section 582.1631 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1631 Potassium hydroxide. (a) Product. Potassium hydroxide. (b) Conditions of use....

  7. 21 CFR 582.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Potassium hydroxide. 582.1631 Section 582.1631 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1631 Potassium hydroxide. (a) Product. Potassium hydroxide. (b) Conditions of use....

  8. 21 CFR 582.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Magnesium hydroxide. 582.1428 Section 582.1428 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1428 Magnesium hydroxide. (a) Product. Magnesium hydroxide. (b) Conditions of use....

  9. 21 CFR 582.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Magnesium hydroxide. 582.1428 Section 582.1428 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1428 Magnesium hydroxide. (a) Product. Magnesium hydroxide. (b) Conditions of use....

  10. 21 CFR 582.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Magnesium hydroxide. 582.1428 Section 582.1428 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1428 Magnesium hydroxide. (a) Product. Magnesium hydroxide. (b) Conditions of use....

  11. 21 CFR 582.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Magnesium hydroxide. 582.1428 Section 582.1428 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1428 Magnesium hydroxide. (a) Product. Magnesium hydroxide. (b) Conditions of use....

  12. 21 CFR 582.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Calcium hydroxide. 582.1205 Section 582.1205 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1205 Calcium hydroxide. (a) Product. Calcium hydroxide. (b) Conditions of use....

  13. 21 CFR 582.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium hydroxide. 582.1205 Section 582.1205 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1205 Calcium hydroxide. (a) Product. Calcium hydroxide. (b) Conditions of use....

  14. 21 CFR 582.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Calcium hydroxide. 582.1205 Section 582.1205 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1205 Calcium hydroxide. (a) Product. Calcium hydroxide. (b) Conditions of use....

  15. 21 CFR 582.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Calcium hydroxide. 582.1205 Section 582.1205 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1205 Calcium hydroxide. (a) Product. Calcium hydroxide. (b) Conditions of use....

  16. 21 CFR 582.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Calcium hydroxide. 582.1205 Section 582.1205 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1205 Calcium hydroxide. (a) Product. Calcium hydroxide. (b) Conditions of use....

  17. 21 CFR 582.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Potassium hydroxide. 582.1631 Section 582.1631 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1631 Potassium hydroxide. (a) Product. Potassium hydroxide. (b) Conditions of use....

  18. 21 CFR 582.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Sodium hydroxide. 582.1763 Section 582.1763 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1763 Sodium hydroxide. (a) Product. Sodium hydroxide. (b) Conditions of use. This...

  19. 21 CFR 582.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sodium hydroxide. 582.1763 Section 582.1763 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1763 Sodium hydroxide. (a) Product. Sodium hydroxide. (b) Conditions of use. This...

  20. 21 CFR 582.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Magnesium hydroxide. 582.1428 Section 582.1428 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1428 Magnesium hydroxide. (a) Product. Magnesium hydroxide. (b) Conditions of use....

  1. 21 CFR 582.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Sodium hydroxide. 582.1763 Section 582.1763 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1763 Sodium hydroxide. (a) Product. Sodium hydroxide. (b) Conditions of use. This...

  2. 21 CFR 582.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Sodium hydroxide. 582.1763 Section 582.1763 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1763 Sodium hydroxide. (a) Product. Sodium hydroxide. (b) Conditions of use. This...

  3. 21 CFR 582.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Sodium hydroxide. 582.1763 Section 582.1763 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1763 Sodium hydroxide. (a) Product. Sodium hydroxide. (b) Conditions of use. This...

  4. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Specific Substances Affirmed as GRAS § 184.1763 Sodium hydroxide. (a) Sodium hydroxide (NaOH, CAS Reg. No... empirical formula is NaOH. Sodium hydroxide is prepared commercially by the electrolysis of sodium chloride... following current good manufacturing practice conditions of use: (1) The ingredient is used as a pH...

  5. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Specific Substances Affirmed as GRAS § 184.1763 Sodium hydroxide. (a) Sodium hydroxide (NaOH, CAS Reg. No... empirical formula is NaOH. Sodium hydroxide is prepared commercially by the electrolysis of sodium chloride... following current good manufacturing practice conditions of use: (1) The ingredient is used as a pH...

  6. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... Specific Substances Affirmed as GRAS § 184.1763 Sodium hydroxide. (a) Sodium hydroxide (NaOH, CAS Reg. No... empirical formula is NaOH. Sodium hydroxide is prepared commercially by the electrolysis of sodium chloride... following current good manufacturing practice conditions of use: (1) The ingredient is used as a pH...

  7. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... Specific Substances Affirmed as GRAS § 184.1763 Sodium hydroxide. (a) Sodium hydroxide (NaOH, CAS Reg. No... empirical formula is NaOH. Sodium hydroxide is prepared commercially by the electrolysis of sodium chloride... following current good manufacturing practice conditions of use: (1) The ingredient is used as a pH...

  8. 21 CFR 582.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Ammonium hydroxide. 582.1139 Section 582.1139 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1139 Ammonium hydroxide. (a) Product. Ammonium hydroxide. (b) Conditions of use....

  9. Anion-π Enzymes

    PubMed Central

    2016-01-01

    In this report, we introduce artificial enzymes that operate with anion-π interactions, an interaction that is essentially new to nature. The possibility to stabilize anionic intermediates and transition states on an π-acidic surface has been recently demonstrated, using the addition of malonate half thioesters to enolate acceptors as a biologically relevant example. The best chiral anion-π catalysts operate with an addition/decarboxylation ratio of 4:1, but without any stereoselectivity. To catalyze this important but intrinsically disfavored reaction stereoselectively, a series of anion-π catalysts was equipped with biotin and screened against a collection of streptavidin mutants. With the best hit, the S112Y mutant, the reaction occurred with 95% ee and complete suppression of the intrinsically favored side product from decarboxylation. This performance of anion-π enzymes rivals, if not exceeds, that of the best conventional organocatalysts. Inhibition of the S112Y mutant by nitrate but not by bulky anions supports that contributions from anion-π interactions exist and matter, also within proteins. In agreement with docking results, K121 is shown to be essential, presumably to lower the pKa of the tertiary amine catalyst to operate at the optimum pH around 3, that is below the pKa of the substrate. Most importantly, increasing enantioselectivity with different mutants always coincides with increasing rates and conversion, i.e., selective transition-state stabilization. PMID:27413782

  10. Anion gap acidosis.

    PubMed

    Ishihara, K; Szerlip, H M

    1998-01-01

    Although an anion gap at less than 20 mEq/L rarely has a defined etiology, significant elevations in the anion gap almost always signify presence of an acidosis that can be easily identified. Anion gap acidoses can be divided into those caused by lactate accumulation, ketoacid production, toxin/drugs, and uremia. Lactic acidoses caused by decreased oxygen delivery or defective oxygen utilization are associated with high mortality. The treatment of lactic acidosis is controversial. The use of bicarbonate to increase pH is rarely successful and, by generating PCO2, may worsen outcome. Ketoacidosis is usually secondary to diabetes or alcohol. Treatment is aimed at turning off ketogenesis and repairing fluid and electrolyte abnormalities. Methanol, ethylene glycol, and salicylates are responsible for the majority of toxin-induced anion gap acidoses. Both methanol and ethylene glycol are associated with severe acidoses and elevated osmolar gaps. Treatment of both is alcohol infusion to decrease formation of toxic metabolites and dialyses to remove toxins. Salicylate toxicity usually is associated with a mild metabolic acidosis and a respiratory alkalosis. Uremia is associated with a mild acidosis secondary to decreased ammonia secretion and an anion gap caused by the retention of unmeasured anions. A decrease in anion gap is caused by numerous mechanisms and thus has little clinical utility.

  11. Anion-π Enzymes.

    PubMed

    Cotelle, Yoann; Lebrun, Vincent; Sakai, Naomi; Ward, Thomas R; Matile, Stefan

    2016-06-22

    In this report, we introduce artificial enzymes that operate with anion-π interactions, an interaction that is essentially new to nature. The possibility to stabilize anionic intermediates and transition states on an π-acidic surface has been recently demonstrated, using the addition of malonate half thioesters to enolate acceptors as a biologically relevant example. The best chiral anion-π catalysts operate with an addition/decarboxylation ratio of 4:1, but without any stereoselectivity. To catalyze this important but intrinsically disfavored reaction stereoselectively, a series of anion-π catalysts was equipped with biotin and screened against a collection of streptavidin mutants. With the best hit, the S112Y mutant, the reaction occurred with 95% ee and complete suppression of the intrinsically favored side product from decarboxylation. This performance of anion-π enzymes rivals, if not exceeds, that of the best conventional organocatalysts. Inhibition of the S112Y mutant by nitrate but not by bulky anions supports that contributions from anion-π interactions exist and matter, also within proteins. In agreement with docking results, K121 is shown to be essential, presumably to lower the pK a of the tertiary amine catalyst to operate at the optimum pH around 3, that is below the pK a of the substrate. Most importantly, increasing enantioselectivity with different mutants always coincides with increasing rates and conversion, i.e., selective transition-state stabilization. PMID:27413782

  12. New layered double hydroxides by prepared by the intercalation of gibbsite

    SciTech Connect

    Rees, Jennifer R.; Burden, Chloe S.; Fogg, Andrew M.

    2015-04-15

    New layered double hydroxides (LDHs) with the composition [MAl{sub 4}(OH){sub 12}]Cl{sub 2}·1.5H{sub 2}O (M=Co, Ni) have been prepared by reacting gibbsite, γ-Al(OH){sub 3}, with the appropriate chloride salt in a synthesis in which the water of crystallization is the only solvent present and fully characterized. These LDHs have been shown to undergo facile anion exchange reactions with both organic and inorganic anions at room temperature making them comparable to other LDHs in this respect. Reactions under the same conditions with CuCl{sub 2}·2H{sub 2}O and ZnCl{sub 2} failed to form the desired LDHs but those with nitrate salts did lead to the formation of the previously reported [MAl{sub 4}(OH){sub 12}](NO{sub 3}){sub 2}·1.5H{sub 2}O (M=Co, Ni) compounds. - Graphical abstract: New layered double hydroxides (LDHs) with the composition [MAl{sub 4}(OH){sub 12}]Cl{sub 2}·1.5H{sub 2}O (M=Co, Ni) have been prepared by reacting gibbsite, γ-Al(OH){sub 3}, with the appropriate chloride salt in a synthesis in which no additional solvent is used and fully characterized. These LDHs have been shown to undergo facile anion exchange reactions with both organic and inorganic anions at room temperature. - Highlights: • Synthesis of new layered double hydroxides, [MAl{sub 4}(OH){sub 12}]Cl{sub 2}·1.5H{sub 2}O (M=Co, Ni). • Demonstration of the anion exchange capacity with both organic and inorganic anions. • Demonstration of the generality of the synthesis for LDHs.

  13. Evaluation of layered zinc hydroxide nitrate and zinc/nickel double hydroxide salts in the removal of chromate ions from solutions

    NASA Astrophysics Data System (ADS)

    de Oliveira, Henrique Bortolaz; Wypych, Fernando

    2016-11-01

    Layered zinc hydroxide nitrate (ZnHN) and Zn/Ni layered double hydroxide salts were synthesized and used to remove chromate ions from solutions at pH 8.0. The materials were characterized by many instrumental techniques before and after chromate ion removal. ZnHN decomposed after contact with the chromate solution, whereas the layered structure of Zn/Ni hydroxide nitrate (Zn/NiHN) and Zn/Ni hydroxide acetate (Zn/NiHA) remained their layers intact after the topotactic anionic exchange reaction, only changing the basal distances. ZnHN, Zn/NiHN, and Zn/NiHA removed 210.1, 144.8, and 170.1 mg of CrO42-/g of material, respectively. Although the removal values obtained for Zn/NiHN and Zn/NiHA were smaller than the values predicted for the ideal formulas of the solids (194.3 and 192.4 mg of CrO42-/g of material, respectively), the measured capacities were higher than the values achieved with many materials reported in the literature. Kinetic experiments showed the removal reaction was fast. To facilitate the solid/liquid separation process after chromium removal, Zn/Ni layered double hydroxide salts with magnetic supports were also synthesized, and their ability to remove chromate was evaluated.

  14. Selective separation of hydroxide from alkaline nuclear tank waste by liquid-liquid extraction with weak hydroxy acids.

    PubMed

    Chambliss, C Kevin; Haverlock, Tamara I; Bonnesen, Peter V; Engle, Nancy L; Moyer, Bruce A

    2002-04-15

    Recovery and recycle of caustic reagents in industrial processes offer potential means of pollution prevention, as investigated herein for particular needs related to the cleanup of alkaline nuclear waste. Specifically, the recovery of hydroxide from alkaline media by liquid-liquid extraction can be effected utilizing weak hydroxy acids, as demonstrated for NaOH utilizing a series of lipophilic fluorinated alcohols and alkylated phenols dissolved in 1-octanol. Extraction efficiency follows the expected order of acidity of the hydroxy acids, the phenols being the most efficient extractants among the compounds tested. After extraction, NaOH is effectively recoverable from the organic phase upon contact with water. The weakest hydroxy acids are the most efficiently stripped, NaOH recovery being nearly quantitative in a single contact. In competitive extraction experiments, good selectivity for hydroxide recovery over other anions such as nitrate and chloride was demonstrated. Since the order of extraction favors larger anions, the exceptional preference for hydroxide implies that the extraction occurs by deprotonation of the hydroxy acids in a cation-exchange process. Stripping therefore occurs by hydrolysis to regenerate the neutral hydroxy acid, liberating NaOH to the aqueous phase. Since hydroxide equivalents rather than actual hydroxide ions are transferred to the solvent, the process is termed "pseudohydroxide extraction." Hydroxide recovery from a simulant of alkaline nuclear tank waste (Hanford DSSF simulant) was also demonstrated in repeated extraction and stripping cycles.

  15. A photochromic thin film based on salicylideneaniline derivatives intercalated layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Wang, Xin Rui; Lu, Jun; Yan, Dongpeng; Wei, Min; Evans, David G.; Duan, Xue

    2010-06-01

    Optically transparent thin films with photochromic properties have been fabricated by means of co-intercalation of azomethine-H anions (AMH) and 1-pentanesulfonate (PS) with different molar ratios into the galleries of a ZnAl layered double hydroxide (LDH). The photochromism of AMH occurred in a 2D confined inorganic matrix has been studied by steady state and transient UV-vis spectroscopy. The AMH anion undergoes an excited-state intramolecular proton transfer from the enol tautomer to trans-keto tautomer after UV excitation, and the relaxed back-isomerization to the ground state of enol tautomer was investigated by transient UV-vis spectroscopy.

  16. Analysis of barium hydroxide and calcium hydroxide slurry carbonation reactors

    SciTech Connect

    Patch, K.D.; Hart, R.P.; Schumacher, W.A.

    1980-05-01

    The removal of CO/sub 2/ from air was investigated by using a continuous-agitated-slurry carbonation reactor containing either barium hydroxide (Ba(OH)/sub 2/) or calcium hydroxide (Ca(OH)/sub 2/). Such a process would be applied to scrub /sup 14/CO/sub 2/ from stack gases at nuclear-fuel reprocessing plants. Decontamination factors were characterized for reactor conditions which could alter hydrodynamic behavior. An attempt was made to characterize reactor performance with models assuming both plug flow and various degrees of backmixing in the gas phase. The Ba(OH)/sub 2/ slurry enabled increased conversion, but apparently the process was controlled under some conditions by phenomena differing from those observed for carbonation by Ca(OH)/sub 2/. Overall reaction mechanisms are postulated.

  17. Impact Of Organic Solvents And Common Anions On 2-Chlorobiphenyl Dechlorination Kinetics With Pd/Mg

    EPA Science Inventory

    The current study evaluates Pd/Mg performance for 2-chlorobiphenyl (2-CB) dechlorination in the presence of naturally abundant anions such as sulfate, chloride, nitrate, hydroxide and carbonates and organic solvents that are used for ex-situ PCB extraction or may accompany PCB co...

  18. Incorporation of phthalocyanines by cationic and anionic clays via ion exchange and direct synthesis

    SciTech Connect

    Carrado, K.A.; Botto, R.E.; Winans, R.E. ); Forman, J.E. )

    1993-04-01

    Phthalocyanines (Pc) and metallophthalocyanines were incorporated into the galleries of anionic and cationic clays via ion exchange and in situ crystallization of the synthetic clay layers. Intercalation compounds between the layered magnesium silicate clay hectorite and cationic phthalocyanines were directly prepared by refluxing for 2 days aqueous solutions of silica sol, magnesium hydroxide, lithium flouride, and either alcian blue dyes (Cu(II)Pc) or 15-crown-5 tetra-substituted phthalocyanine (15C5Pc). The CuPc dyes are tetrapositively charged through peripheral quaternary ammonium groups, whereas the 15C5Pc is electrically neutral. Anionic clays prepared by hydrolysis of mixed solutions of aluminum nitrate, magnesium nitrate, and copper(II) phthalocyaninetetrasulfonic acid, tetrasodium salt (CuPcTs) in sodium hydroxide resulted in crystallization of an intercalation compound between a layered double hydroxide (LDH) and this anionic Pc. The material prepared by ion exchange of CuPcTs into a wet, freshly prepared LDH was superior in crystallinity. The phthalocyanines are oriented parallel to cationic hectorite clay layers (gallery heights 4.5-6.5[angstrom]) and perpendicular to anionic layered double hydroxide clay layers (gallery height 18,2[angstrom]) in correlation with their hosts' respective layer charge densities. 32 refs., 4 figs., 2 tabs.

  19. Intrinsic anion oxidation potentials.

    PubMed

    Johansson, Patrik

    2006-11-01

    Anions of lithium battery salts have been investigated by electronic structure calculations with the objective to find a computational measure to correlate with the observed (in)stability of nonaqueous lithium battery electrolytes vs oxidation often encountered in practice. Accurate prediction of intrinsic anion oxidation potentials is here made possible by computing the vertical free energy difference between anion and neutral radical (Delta Gv) and further strengthened by an empirical correction using only the anion volume as a parameter. The 6-311+G(2df,p) basis set, the VSXC functional, and the C-PCM SCRF algorithm were used. The Delta Gv calculations can be performed using any standard computational chemistry software. PMID:17078600

  20. Anion exchange polymer electrolytes

    SciTech Connect

    Kim, Yu Seung; Kim, Dae Sik

    2015-06-02

    Anion exchange polymer electrolytes that include guanidinium functionalized polymers may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

  1. Tunable Electronic Transport Properties of 2D Layered Double Hydroxide Crystalline Microsheets with Varied Chemical Compositions.

    PubMed

    Zhao, Yibing; Hu, Hai; Yang, Xiaoxia; Yan, Dongpeng; Dai, Qing

    2016-09-01

    Transistors based on layered double hydroxides (LDH) single microcrystal are fabricated, whose conductivity of LDH can be tuned by varying metal cations or interlayer anions, but weakly affected by external electric field. The carrier mobility can reach about 1 × 10(-5) cm(2) V(-1) s(-1) , a value comparable to that of organic C60-based transistors. This work paves a way for future electrical applications of LDH. PMID:27416544

  2. CdCu{sub 3}(OH){sub 6}Cl{sub 2}: A new layered hydroxide chloride

    SciTech Connect

    McQueen, T.M.; Han, T.H.; Freedman, D.E.; Stephens, P.W.; Lee, Y.S.; Nocera, D.G.

    2011-12-15

    A new transition metal hydroxide chloride containing kagome layers of magnetic ions, CdCu{sub 3}(OH){sub 6}Cl{sub 2}, has been synthesized and structurally characterized. The actual low symmetry P2{sub 1}/n structure can be derived from the ideal trigonal one with a change in cation distribution and coherent distortions of the anion framework. The result is a fundamentally different Cu{sup 2+} kagome framework than found in the related Herbertsmithite and Kapellasite minerals. Magnetization measurements show no transition to long range magnetic order above T=2 K, despite strong antiferromagnetic interactions with a Weiss temperature of {theta}{sub w}=-150 K. Furthermore, we show that the structure of CdCu{sub 3}(OH){sub 6}Cl{sub 2} and related hydroxide chlorides can be rationalized on the basis of [(OH){sub 3}Cl]{sup 4-} pseudopolyatomic anions that pack and rotate, in much the same way as do traditional polyatomic anions. This opens the door to rational design of new and useful hydroxide chloride materials. - Graphical Abstract: The [(OH){sub 3}Cl]{sup 4-} pseudopolyatomic anion and the kagome lattice of CdCu{sub 3}[(OH){sub 3}Cl]{sub 2}. Highlights: Black-Right-Pointing-Pointer A new understanding of hydroxide chlorides, based on the polyatomic anion [(OH){sub 3}Cl]{sup 4-}. Black-Right-Pointing-Pointer Synthesis and structure of a new layered hydroxide chloride, CdCu{sub 3}(OH){sub 6}Cl{sub 2}, are reported. Black-Right-Pointing-Pointer A new compound is reported with kagome layers of Cu{sup 2+}.

  3. Structures and properties of anionic clay minerals

    NASA Astrophysics Data System (ADS)

    Koch, Chr. Bender

    1998-12-01

    The Mössbauer spectra of pyroaurite-sjögrenite-type compounds (PTC) (layered anion exchangers) are discussed with reference to the crystal structure, cation order, and crystallite morphology. It is shown that cation-ordered layers are produced in the synthesis of carbonate and sulphate types of green rust. In contrast, synthetic and natural pyroaurite only occurs as disordered types. The redox chemistry of Fe(III) within the metal hydroxide layer is illustrated with examples of electrochemical oxidation and reversible reduction by boiling glycerol. The chemistry of iron in the interlayer is exemplified by the intercalation of Fe-cyanide complexes in hydrotalcite. This reaction may be used as a probe for the charge distribution in the interlayer.

  4. Hydroxide based Benzyltrimethylammonium degradation: Quantification of rates and degradation technique development

    DOE PAGES

    Sturgeon, Matthew R.; Macomber, Clay S.; Engtrakul, Chaiwat; Long, Hai; Pivovar, Bryan S.

    2015-01-21

    Anion exchange membranes (AEMs) are of interest as hydroxide conducting polymer electrolytes in electrochemical devices like fuel cells and electrolyzers. AEMs require hydroxide stable covalently tetherable cations to ensure required conductivity. Benzyltrimethylammonium (BTMA) has been the covalently tetherable cation that has been most often employed in anion exchange membranes because it is reasonably basic, compact (limited number of atoms per charge), and easily/cheaply synthesized. Several reports exist that have investigated hydroxide stability of BTMA under specific conditions, but consistency within these reports and comparisons between them have not yet been made. While the hydroxide stability of BTMA has been believedmore » to be a limitation for AEMs, this stability has not been thoroughly reported. In this paper, we have found that several methods reported have inherent flaws in their findings due to the difficulty of performing degradation experiments at high temperature and high pH. In order to address these shortcomings, we have developed a reliable, standardized method of determining cation degradation under conditions similar/relevant to those expected in electrochemical devices. The experimental method has been employed to determine BTMA stabilities at varying cation concentrations and elevated temperatures, and has resulted in improved experimental accuracy and reproducibility. Finally and most notably, these results have shown that BTMA is quite stable at 80°C (half-life of ~4 years), a significant increase in stability over what had been reported previously.« less

  5. Hydroxide based Benzyltrimethylammonium degradation: Quantification of rates and degradation technique development

    SciTech Connect

    Sturgeon, Matthew R.; Macomber, Clay S.; Engtrakul, Chaiwat; Long, Hai; Pivovar, Bryan S.

    2015-01-21

    Anion exchange membranes (AEMs) are of interest as hydroxide conducting polymer electrolytes in electrochemical devices like fuel cells and electrolyzers. AEMs require hydroxide stable covalently tetherable cations to ensure required conductivity. Benzyltrimethylammonium (BTMA) has been the covalently tetherable cation that has been most often employed in anion exchange membranes because it is reasonably basic, compact (limited number of atoms per charge), and easily/cheaply synthesized. Several reports exist that have investigated hydroxide stability of BTMA under specific conditions, but consistency within these reports and comparisons between them have not yet been made. While the hydroxide stability of BTMA has been believed to be a limitation for AEMs, this stability has not been thoroughly reported. In this paper, we have found that several methods reported have inherent flaws in their findings due to the difficulty of performing degradation experiments at high temperature and high pH. In order to address these shortcomings, we have developed a reliable, standardized method of determining cation degradation under conditions similar/relevant to those expected in electrochemical devices. The experimental method has been employed to determine BTMA stabilities at varying cation concentrations and elevated temperatures, and has resulted in improved experimental accuracy and reproducibility. Finally and most notably, these results have shown that BTMA is quite stable at 80°C (half-life of ~4 years), a significant increase in stability over what had been reported previously.

  6. Interfacial solvation thermodynamics.

    PubMed

    Ben-Amotz, Dor

    2016-10-19

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air-water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute-solvent) and indirect (solvent-solvent) contributions to adsorption thermodynamics, of relevance to solvation at air-water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. PMID:27545849

  7. Interfacial solvation thermodynamics

    NASA Astrophysics Data System (ADS)

    Ben-Amotz, Dor

    2016-10-01

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air-water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute-solvent) and indirect (solvent-solvent) contributions to adsorption thermodynamics, of relevance to solvation at air-water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies.

  8. Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Fernández, Ariel

    2015-10-01

    The spontaneous negative charging of aqueous nonpolar interfaces has eluded quantitative first-principle prediction, possibly because it steadfastly challenges the classical Debye dielectric picture. In this work we show that quantitative prediction requires a substantive revision of Debye's linear dielectric ansatz to incorporate an anomalous polarization component yielding electrostatic energy stored as interfacial tension and detailed enough to account for the differences in electronic structure between water and its ionized states. The minimization of this interfacial tension is due to a quantum effect resulting in the reduction in hydrogen-bond frustration that takes place upon hydroxide ion adsorption. The quantitative predictions are validated vis-à-vis measurements of the free energy change associated with hydroxide adsorption obtained using sum-frequency vibrational spectroscopy.

  9. Effect of nanoscale patterned interfacial roughness on interfacial toughness.

    SciTech Connect

    Zimmerman, Jonathan A.; Moody, Neville Reid; Mook, William M.; Kennedy, Marian S.; Bahr, David F.; Zhou, Xiao Wang; Reedy, Earl David, Jr.

    2007-09-01

    The performance and the reliability of many devices are controlled by interfaces between thin films. In this study we investigated the use of patterned, nanoscale interfacial roughness as a way to increase the apparent interfacial toughness of brittle, thin-film material systems. The experimental portion of the study measured the interfacial toughness of a number of interfaces with nanoscale roughness. This included a silicon interface with a rectangular-toothed pattern of 60-nm wide by 90-nm deep channels fabricated using nanoimprint lithography techniques. Detailed finite element simulations were used to investigate the nature of interfacial crack growth when the interface is patterned. These simulations examined how geometric and material parameter choices affect the apparent toughness. Atomistic simulations were also performed with the aim of identifying possible modifications to the interfacial separation models currently used in nanoscale, finite element fracture analyses. The fundamental nature of atomistic traction separation for mixed mode loadings was investigated.

  10. Highly Conductive Anion-Exchange Membranes from Microporous Tröger's Base Polymers.

    PubMed

    Yang, Zhengjin; Guo, Rui; Malpass-Evans, Richard; Carta, Mariolino; McKeown, Neil B; Guiver, Michael D; Wu, Liang; Xu, Tongwen

    2016-09-12

    The development of polymeric anion-exchange membranes (AEMs) combining high ion conductivity and long-term stability is a major challenge for materials chemistry. AEMs with regularly distributed fixed cationic groups, based on the formation of microporous polymers containing the V-shape rigid Tröger's base units, are reported for the first time. Despite their simple preparation, which involves only two synthetic steps using commercially available precursors, the polymers provide AEMs with exceptional hydroxide conductivity at relatively low ion-exchange capacity, as well as a high swelling resistance and chemical stability. An unprecedented hydroxide conductivity of 164.4 mS cm(-1) is obtained at a relatively a low ion-exchange capacity of 0.82 mmol g(-1) under optimal operating conditions. The exceptional anion conductivity appears related to the intrinsic microporosity of the charged polymer matrix, which facilitates rapid anion transport. PMID:27505421

  11. Anion-π catalysis.

    PubMed

    Zhao, Yingjie; Beuchat, César; Domoto, Yuya; Gajewy, Jadwiga; Wilson, Adam; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2014-02-01

    The introduction of new noncovalent interactions to build functional systems is of fundamental importance. We here report experimental and theoretical evidence that anion-π interactions can contribute to catalysis. The Kemp elimination is used as a classical tool to discover conceptually innovative catalysts for reactions with anionic transition states. For anion-π catalysis, a carboxylate base and a solubilizer are covalently attached to the π-acidic surface of naphthalenediimides. On these π-acidic surfaces, transition-state stabilizations up to ΔΔGTS = 31.8 ± 0.4 kJ mol(-1) are found. This value corresponds to a transition-state recognition of KTS = 2.7 ± 0.5 μM and a catalytic proficiency of 3.8 × 10(5) M(-1). Significantly increasing transition-state stabilization with increasing π-acidity of the catalyst, observed for two separate series, demonstrates the existence of "anion-π catalysis." In sharp contrast, increasing π-acidity of the best naphthalenediimide catalysts does not influence the more than 12 000-times weaker substrate recognition (KM = 34.5 ± 1.6 μM). Together with the disappearance of Michaelis-Menten kinetics on the expanded π-surfaces of perylenediimides, this finding supports that contributions from π-π interactions are not very important for anion-π catalysis. The linker between the π-acidic surface and the carboxylate base strongly influences activity. Insufficient length and flexibility cause incompatibility with saturation kinetics. Moreover, preorganizing linkers do not improve catalysis much, suggesting that the ideal positioning of the carboxylate base on the π-acidic surface is achieved by intramolecular anion-π interactions rather than by an optimized structure of the linker. Computational simulations are in excellent agreement with experimental results. They confirm, inter alia, that the stabilization of the anionic transition states (but not the neutral ground states) increases with the π-acidity of the

  12. Anion-π catalysis.

    PubMed

    Zhao, Yingjie; Beuchat, César; Domoto, Yuya; Gajewy, Jadwiga; Wilson, Adam; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2014-02-01

    The introduction of new noncovalent interactions to build functional systems is of fundamental importance. We here report experimental and theoretical evidence that anion-π interactions can contribute to catalysis. The Kemp elimination is used as a classical tool to discover conceptually innovative catalysts for reactions with anionic transition states. For anion-π catalysis, a carboxylate base and a solubilizer are covalently attached to the π-acidic surface of naphthalenediimides. On these π-acidic surfaces, transition-state stabilizations up to ΔΔGTS = 31.8 ± 0.4 kJ mol(-1) are found. This value corresponds to a transition-state recognition of KTS = 2.7 ± 0.5 μM and a catalytic proficiency of 3.8 × 10(5) M(-1). Significantly increasing transition-state stabilization with increasing π-acidity of the catalyst, observed for two separate series, demonstrates the existence of "anion-π catalysis." In sharp contrast, increasing π-acidity of the best naphthalenediimide catalysts does not influence the more than 12 000-times weaker substrate recognition (KM = 34.5 ± 1.6 μM). Together with the disappearance of Michaelis-Menten kinetics on the expanded π-surfaces of perylenediimides, this finding supports that contributions from π-π interactions are not very important for anion-π catalysis. The linker between the π-acidic surface and the carboxylate base strongly influences activity. Insufficient length and flexibility cause incompatibility with saturation kinetics. Moreover, preorganizing linkers do not improve catalysis much, suggesting that the ideal positioning of the carboxylate base on the π-acidic surface is achieved by intramolecular anion-π interactions rather than by an optimized structure of the linker. Computational simulations are in excellent agreement with experimental results. They confirm, inter alia, that the stabilization of the anionic transition states (but not the neutral ground states) increases with the π-acidity of the

  13. Regeneration of strong-base anion-exchange resins by sequential chemical displacement

    DOEpatents

    Brown, Gilbert M.; Gu, Baohua; Moyer, Bruce A.; Bonnesen, Peter V.

    2002-01-01

    A method for regenerating strong-base anion exchange resins utilizing a sequential chemical displacement technique with new regenerant formulation. The new first regenerant solution is composed of a mixture of ferric chloride, a water-miscible organic solvent, hydrochloric acid, and water in which tetrachloroferrate anion is formed and used to displace the target anions on the resin. The second regenerant is composed of a dilute hydrochloric acid and is used to decompose tetrachloroferrate and elute ferric ions, thereby regenerating the resin. Alternative chemical displacement methods include: (1) displacement of target anions with fluoroborate followed by nitrate or salicylate and (2) displacement of target anions with salicylate followed by dilute hydrochloric acid. The methodology offers an improved regeneration efficiency, recovery, and waste minimization over the conventional displacement technique using sodium chloride (or a brine) or alkali metal hydroxide.

  14. Spectral induced polarization signatures of hydroxide adsorption and mineral precipitation in porous media

    SciTech Connect

    Chi Zhang; Lee Slater; George Redden; Yoshiko Fujita; Timothy Johnson; Don Fox

    2012-04-01

    The spectral induced polarization (SIP) technique is a promising approach for delineating subsurface physical and chemical property changes in a minimally invasive manner. We investigated spatiotemporal variations in complex conductivity during evolution of urea hydrolysis and calcite precipitation reaction fronts within a silica gel column. The real and imaginary parts of complex conductivity were shown to be sensitive to changes in both solution chemistry and calcium carbonate precipitation. Distinct changes in imaginary conductivity coincided with increased hydroxide ion concentration during urea hydrolysis. In a separate experiment focused on the effect of hydroxide concentration on interfacial polarization of silica gel and well-sorted sand, we found a strong dependence of the polarization response on pH changes of the solution. We propose a conceptual model describing hydroxide ion adsorption behavior in silica gel and its control on interfacial polarizability. Our results demonstrate the utility of SIP for non-invasive monitoring of reaction fronts, and indicate its potential for quantifying geochemical processes that control the polarization responses of porous media at larger spatial scales in the natural environment.

  15. Spectral Induced Polarization Signatures of Hydroxide Adsorption and Mineral Precipitation in Porous Media

    SciTech Connect

    Zhang, Chi; Slater, Lee; Redden, George D.; Fujita, Yoshiko; Johnson, Timothy C.; Fox, Don

    2012-04-17

    The spectral induced polarization (SIP) technique is a promising approach for delineating subsurface physical and chemical property changes in a minimally invasive manner. To facilitate the understanding of position and chemical properties of reaction fronts that involve mineral precipitation in porous media, we investigated spatiotemporal variations in complex conductivity during evolution of urea hydrolysis and calcite precipitation reaction fronts within a silica gel column. The real and imaginary parts of complex conductivity were shown to be sensitive to changes in both solution chemistry and calcium carbonate precipitation. Distinct changes in imaginary conductivity coincided with increased hydroxide ion concentration during urea hydrolysis. In a separate experiment focused on the effect of hydroxide concentration on interfacial polarization of silica gel and well-sorted sand, we found a significant dependence of the polarization response on pH changes of the solution. We propose a conceptual model describing hydroxide ion adsorption behavior in silica gel and its control on interfacial polarizability. Our results demonstrate the utility of SIP for noninvasive monitoring of reaction fronts, and indicate its potential for quantifying geochemical processes that control the polarization responses of porous media at larger spatial scales in the natural environment.

  16. Adsorption of DNA onto anionic lipid surfaces.

    PubMed

    Martín-Molina, Alberto; Luque-Caballero, Germán; Faraudo, Jordi; Quesada-Pérez, Manuel; Maldonado-Valderrama, Julia

    2014-04-01

    Currently self-assembled DNA delivery systems composed of DNA multivalent cations and anionic lipids are considered to be promising tools for gene therapy. These systems become an alternative to traditional cationic lipid-DNA complexes because of their low cytotoxicity lipids. However, currently these nonviral gene delivery methods exhibit low transfection efficiencies. This feature is in large part due to the poorly understood DNA complexation mechanisms at the molecular level. It is well-known that the adsorption of DNA onto like charged lipid surfaces requires the presence of multivalent cations that act as bridges between DNA and anionic lipids. Unfortunately, the molecular mechanisms behind such adsorption phenomenon still remain unclear. Accordingly a historical background of experimental evidence related to adsorption and complexation of DNA onto anionic lipid surfaces mediated by different multivalent cations is firstly reviewed. Next, recent experiments aimed to characterise the interfacial adsorption of DNA onto a model anionic phospholipid monolayer mediated by Ca(2+) (including AFM images) are discussed. Afterwards, modelling studies of DNA adsorption onto charged surfaces are summarised before presenting preliminary results obtained from both CG and all-atomic MD computer simulations. Our results allow us to establish the optimal conditions for cation-mediated adsorption of DNA onto negatively charged surfaces. Moreover, atomistic simulations provide an excellent framework to understand the interaction between DNA and anionic lipids in the presence of divalent cations. Accordingly,our simulation results in conjunction go beyond the macroscopic picture in which DNA is stuck to anionic membranes by using multivalent cations that form glue layers between them. Structural aspects of the DNA adsorption and molecular binding between the different charged groups from DNA and lipids in the presence of divalent cations are reported in the last part of the study

  17. Manipulating Ordering Transitions in Interfacially Modified Block Copolymers

    SciTech Connect

    Singh, N.; Tureau, M; Epps, T

    2009-01-01

    We report a synthetic strategy that allows us to manipulate the interfacial region between blocks and control ordering transitions in poly(isoprene-b-styrene) [P(I-S)] block copolymers. This interfacial modification is accomplished by combining a semi-batch feed with anionic polymerization techniques. Using this approach, we are able to control the segmental composition and molecular interactions in our phase-separated block copolymers, independent of molecular weight and block constituents. A library of copolymers is prepared with various interfacial modifications to examine the effect of interfacial composition on copolymer self-assembly. The morphological characteristics of the self-assembled structures are investigated using small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA). Normal and inverse tapered block copolymers, containing approximately 15-35 vol% tapered material, show a measurable decrease in the order-disorder transition temperature (TODT) relative to the corresponding non-tapered diblock copolymers, with the inverse tapered materials showing the greatest deviation in TODT. Additionally, TODT was inversely related to the volume fraction of the tapered region in both normal and inverse tapered copolymer materials.

  18. More About Measuring Interfacial Tension Between Liquids

    NASA Technical Reports Server (NTRS)

    Rashidnia, Nasser; Balasubramaniam, R.; Del Signore, David M.

    1995-01-01

    Report presents additional discussion of technique for measuring interfacial tension between two immiscible liquids. Technique described in "Measuring Interfacial Tension Between Immiscible Liquids" (LEW-15855).

  19. Layered rare earth hydroxides (LREHs): synthesis and structure characterization towards multifunctionality.

    PubMed

    Liang, Jianbo; Ma, Renzhi; Sasaki, Takayoshi

    2014-07-21

    Layered rare earth hydroxides (LREHs) represent a new family of layered host compounds that integrate attractive physicochemical properties of rare earth elements with the wide tunability of guest anions. The compounds have attracted significant research attention, and potential applications have been found in various fields such as optics, catalysis, bio-medicine and so on. In this perspective, we describe our recent progress in the synthesis, structure characterization, and development of functionalities of the LREH compounds. A unique homogeneous alkalization method, in which RE ions are precipitated from a solution containing RE salt, concentrated target anions and hexamethylenetetramine, has been employed to effectively produce highly crystalline LREH samples. A range of anionic forms including chloride-, nitrate-, sulfate- and organodisulfonate-series, have been synthesized and structurally characterized. Two types of cationic rare earth hydroxide layers, {[RE2(OH)5(H2O)2](+)}∞ for the chloride- and nitrate-series and {[RE(OH)2(H2O)](+)}∞ for the sulfate- and organodisulfonate-series, are classified. Unique dehydration/rehydration behaviors or thermal phase evolution of the LREH compounds have been revealed and discussed in relation to the crystal structures. An outlook for potential applications of LREH compounds as anion exchangers, precursors to unique functional oxides, and optical phosphors is described. PMID:24824303

  20. Enhanced thermal- and photo-stability of acid yellow 17 by incorporation into layered double hydroxides

    SciTech Connect

    Wang Qian; Feng Yongjun; Feng Junting; Li Dianqing

    2011-06-15

    2,5-dichloro-4-(5-hydroxy-3-methyl-4-(sulphophenylazo) pyrazol-1-yl) benzenesulphonate (DHSB) anions, namely acid yellow 17 anions, have been successfully intercalated into Zn-Al layered double hydroxides (LDH) to produce a novel organic-inorganic pigment by a simple method involving separate nucleation and aging steps (SNAS), and the dye-intercalated LDH was analyzed by various techniques, e.g., XRD, SEM, FT-IR, TG-DTA and ICP. The d-spacing of the prepared LDH is 2.09 nm. Furthermore, the incorporation of the DHSB aims to enhance the thermal- and photo-stability of the guest dye molecule, for example, the less color change after accelerated thermal- and photo-aging test. - Graphical abstract: Acid yellow anions were successfully assembled into ZnAl layered double hydroxides (LDH) to produce a novel organic-inorganic composite pigment by a simple method involving separate nucleation and aging steps (SNAS). Highlights: > Acid yellow 17 was directly intercalated into ZnAl-LDH to form a novel pigment. > The pigment was prepared by a method involving separate nucleation and aging steps. > The intercalation of dye anions enhances its thermal- and photo-stability.

  1. APPLICATIONS OF LAYERED DOUBLE HYDROXIDES IN REMOVING OXYANIONS FROM OIL REFINING AND COAL MINING WASTEWATER

    SciTech Connect

    Song Jin; Paul Fallgren

    2006-03-01

    Western Research Institute (WRI), in conjunction with the U.S. Department of Energy (DOE), conducted a study of using the layered double hydroxides (LDH) as filter material to remove microorganisms, large biological molecules, certain anions and toxic oxyanions from various waste streams, including wastewater from refineries. Results demonstrate that LDH has a high adsorbing capability to those compounds with negative surface charge. Constituents studied include model bacteria, viruses, arsenic, selenium, vanadium, diesel range hydrocarbons, methyl tert-butyl ether (MTBE), mixed petroleum constituents, humic materials and anions. This project also attempted to modify the physical structure of LDH for the application as a filtration material. Flow characterizations of the modified LDH materials were also investigated. Results to date indicate that LDH is a cost-effective new material to be used for wastewater treatment, especially for the treatment of anions and oxyanions.

  2. Mechanisms of mineral membrane fouling growth modulated by pulsed modes of current during electrodialysis: evidences of water splitting implications in the appearance of the amorphous phases of magnesium hydroxide and calcium carbonate.

    PubMed

    Cifuentes-Araya, Nicolás; Astudillo-Castro, Carolina; Bazinet, Laurent

    2014-07-15

    Experiments revealed the fouling nature evolutions along different electrodialysis (ED) trials, and how it disappears when current pulsation acts repetitively on the interfaces of ion-exchange membranes (IEMs). Fouling was totally controlled on the diluate side of cation-exchange membrane (CEM) by the repetitive pulsation frequency of the higher on-duty ratios applied. They created steady water splitting proton-barriers that neutralized OH(-) leakage through the membrane, decreasing the interfacial pH, and fouling of the concentrate side. The anion-exchange membrane (AEM) on the diluate side was similarly protected, but it was fouled once water splitting OH(-) generation became either intense enough or excessively weak. Interestingly, amorphous magnesium hydroxide (AMH) stemmed on the CEM-diluate side from brucite under intense water splitting OH(-) generation, and/or strong OH(-) leakage electromigration through the membrane. Water dissociation and overlimiting current regimes triggered drastic water molecule removal from crystal lattices through an accelerated cascade water splitting reaction. Also, amorphous calcium carbonate (ACC) appeared on CEM under intense water splitting reaction, and disappeared once intense OH(-) leakage was allowed by the water splitting proton-barrier dissipation. Our findings have implications for membrane fouling control, as well as for the understanding of the growth behavior of CaCO3 and Mg(OH)2 species on electromembrane interfaces.

  3. Interfacial Effects in Polymer Membranes for Clean Energy

    NASA Astrophysics Data System (ADS)

    Soles, Christopher

    2013-03-01

    Polymeric membranes are critical components in several emerging clean energy technologies. Examples include proton exchange membranes for hydrogen fuel cells, anion exchange membranes for alkaline fuel cells, flow batteries, and even block copolymer membranes for solid electrolytes/separators in lithium ion and other battery technologies. In all of these examples the function of the membrane is to physically separate two reactive electrodes or reactants, but allow the transport or exchange of specific ions through the membrane between the active electrodes. The flow of the charged ionic species between the electrodes can be used to balance the flow of electrons through an external electrical circuit that connects the electrodes, thereby storing or delivering charge electrochemically. In this presentation I will review the use of polymeric membranes in electrochemical energy storage technologies and discuss the critical issues related to the membranes that hinder these technologies. In particular I will also focus on the role the polymer membrane interface on device performance. At some point the polymer membrane must be interfaced with an active electrode or catalyst and the nature of this interface can significantly impact performance. Simulations of device performance based on bulk membrane transport properties often fail to predict the actual performance and empirical interfacial impedance terms usually added to capture the device performance. In this presentation I will explore the origins of this interfacial impedance in the different types of fuel cell membranes (proton and alkaline) by creating model thin film membranes where all of the membrane can be considered interfacial. We then use these thin films as a surrogate for the interfacial regions of a bulk membrane and then quantify the structure, dynamics, and transport properties of water and ions in the confined interfacial films. Using neutron reflectivity, grazing incidence X-ray diffraction, and

  4. Bonding by Hydroxide-Catalyzed Hydration and Dehydration

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung

    2008-01-01

    A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to

  5. Preparation of anionic clay-birnessite manganese oxide composites by interlayer oxidation of oxalate ions by permanganate

    SciTech Connect

    Arulraj, James; Rajamathi, Michael

    2013-02-15

    Oxalate intercalated anionic clay-like nickel zinc hydroxysalt was obtained starting from nickel zinc hydroxyacetate, Ni{sub 3}Zn{sub 2}(OH){sub 8}(OAc){sub 2}{center_dot}2H{sub 2}O, by anion exchange. The intercalated oxalate species was reacted with potassium permanganate in such a way that the layered manganese oxide formed was within the interlayer region of the anionic clay resulting in a layered composite in which the negative charges on the birnessite type manganese oxide layers compensate the positive charges on the anionic clay layers. Birnessite to anionic clay ratio could be varied by varying the reaction time or the amount of potassium permanganate used. - Graphical abstract: Nickel zinc hydroxyoxalate was reacted with potassium permanganate to get nickel zinc hydroxide birnessite composites in which the positive charges on the hydroxide layers are neutralized by the negative charges on birnessite layers. Highlights: Black-Right-Pointing-Pointer Anionic and cationic layered solid composites prepared. Black-Right-Pointing-Pointer Ni-Zn hydroxyoxalate reacted with KMnO{sub 4} to deposit MnO{sub 2} in the interlayer. Black-Right-Pointing-Pointer Birnessite layers coexist with anionic clay layers in the composites. Black-Right-Pointing-Pointer Birnessite/anionic clay ratio controlled by amount of KMnO{sub 4} used and reaction time.

  6. 21 CFR 184.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... GRAS § 184.1428 Magnesium hydroxide. (a) Magnesium hydroxide (Mg(OH)2, CAS Reg. No. 1309-42-8) occurs... magnesium oxide. (b) The ingredient meets the specifications of the Food Chemicals Codex, 3d Ed. (1981), p...: (1) The ingredient is used as a nutrient supplement as defined in § 170.3(o)(20) of this chapter; a...

  7. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... GRAS § 184.1763 Sodium hydroxide. (a) Sodium hydroxide (NaOH, CAS Reg. No. 1310-73-2) is also known as sodium hydrate, soda lye, caustic soda, white caustic, and lye. The empirical formula is NaOH. Sodium... manufacturing practice conditions of use: (1) The ingredient is used as a pH control agent as defined in §...

  8. Interfacial behavior of perchlorate versus chloride ions in saturated aqueous salt solutions

    SciTech Connect

    Ghosal, S; Kuo, I W; Baer, M D; Bluhm, H

    2009-04-14

    In recent years combination of theoretical and experimental work have presented a novel view of the aqueous interface wherein hard and/or multiply charged ions are excluded from the interface, but large polarizable anions show interfacial enhancement relative to the bulk. The observed trend in the propensity of anions to adsorb at the air/water interface appears to be reverse of the Hofmeister series for anions. This study focuses on experimental and theoretical examination of the partitioning behavior of perchlorate (ClO{sub 4}{sup -}) and chloride (Cl{sup -}) ions at the air/water interface. We have used ambient pressure X-ray photoelectron spectroscopy technique to directly probe the interfacial concentrations of ClO{sub 4}{sup -} and Cl{sup -} ions in sodium perchlorate and sodium chloride solutions, respectively. Experimental observations are compared with first principles molecular dynamics simulations. Both experimental and simulation results show enhancement of ClO{sub 4}{sup -} ion at the interface, compared with the absence of such enhancement in the case of Cl{sup -} ion. These observations are in agreement with the expected trend in the interfacial propensity of anions based on the Hofmeister series.

  9. Molten Hydroxide Trapping Process for Radioiodine

    SciTech Connect

    Trowbridge, L.D.

    2003-01-28

    A molten hydroxide trapping process has been considered for removing radioiodine species from off-gas streams whereby iodine is reacted directly with molten hydroxides such as NaOH or KOH. The resulting product is the corresponding iodide, which can be separated by simple cooling of the molten mixture to grow the iodide primary phase once the mixture reaches 70-80 mol% in the iodide component. Thermodynamic analysis indicates that such a chemical process is highly favorable. Experimental testing of the trapping process using molecular iodine showed trapping of up to 96% of the volatile iodine. The trapping efficiency was dependent on operational parameters such as temperature and gas-melt contact efficiency, and higher efficiencies are expected as the process is further developed. While an iodide phase could be effectively isolated by slow cooling of a molten iodide-hydroxide mixture, the persistent appearance of hydroxide indicated that an appreciable solubility of hydroxide occurred in the iodide phase.

  10. Pretreatment of rapeseed straw by sodium hydroxide.

    PubMed

    Kang, Kyeong Eop; Jeong, Gwi-Taek; Park, Don-Hee

    2012-06-01

    Pretreatment method for rapeseed straw by sodium hydroxide was investigated for production of bioethanol and biobutanol. Various pretreatment parameters, including temperature, time, and sodium hydroxide concentration were optimized using a statistical method which is a central composite design of response surface methodology. In the case of sodium hydroxide pretreatment, optimal pretreatment conditions were found to be 7.9% sodium hydroxide concentration, 5.5 h of reaction time, and 68.4 °C of reaction temperature. The maximum glucose yield which can be recovered by enzymatic hydrolysis at the optimum conditions was 95.7% and the experimental result was 94.0 ± 4.8%. This experimental result was in agreement with the model prediction. An increase of surface area and pore size in pretreated rapeseed straw by sodium hydroxide pretreatment was observed by scanning electron microscope.

  11. High temperature interfacial superconductivity

    SciTech Connect

    Bozovic, Ivan; Logvenov, Gennady; Gozar, Adrian Mihai

    2012-06-19

    High-temperature superconductivity confined to nanometer-scale interfaces has been a long standing goal because of potential applications in electronic devices. The spontaneous formation of a superconducting interface in bilayers consisting of an insulator (La.sub.2CuO.sub.4) and a metal (La.sub.1-xSr.sub.xCuO.sub.4), neither of which is superconducting per se, is described. Depending upon the layering sequence of the bilayers, T.sub.c may be either .about.15 K or .about.30 K. This highly robust phenomenon is confined to within 2-3 nm around the interface. After exposing the bilayer to ozone, T.sub.c exceeds 50 K and this enhanced superconductivity is also shown to originate from a 1 to 2 unit cell thick interfacial layer. The results demonstrate that engineering artificial heterostructures provides a novel, unconventional way to fabricate stable, quasi two-dimensional high T.sub.c phases and to significantly enhance superconducting properties in other superconductors. The superconducting interface may be implemented, for example, in SIS tunnel junctions or a SuFET.

  12. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  13. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

    1984-01-01

    Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

  14. Anion permselective membrane

    NASA Astrophysics Data System (ADS)

    Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

    1984-07-01

    Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

  15. Anion Exchange Membranes: Current Status and Moving Forward

    SciTech Connect

    Hickner, MA; Herring, AM; Coughlin, EB

    2013-10-29

    This short review is meant to provide the reader with highlights in anion exchange membrane research, describe current needs in the field, and point out promising directions for future work. Anion exchange membranes (AEMs) provide one possible route to low platinum or platinum-free fuel cells with the potential for facile oxidation of complex fuels beyond hydrogen and methanol. AEMs and related stable cationic polymers also have applications in energy storage and other electrochemical technologies such as water electrolyzers and redox flow batteries. While anion exchange membranes have been known for a long time in water treatment applications, materials for electrochemical technology with robust mechanical properties in thin film format have only recently become more widely available. High hydroxide and bicarbonate anion conductivity have been demonstrated in a range of AEM formats, but intrinsic stability of the polymers and demonstration of long device lifetime remain major roadblocks. Novel approaches to stable materials have focused on new types of cations that employ delocalization and steric shielding of the positive center to mitigate nucleophilic attack by hydroxide. A number of promising polymer backbones and membrane architectures have been identified, but limited device testing and a lack of understanding of the degradation mechanisms in operating devices is slowing progress on engineered systems with alkaline fuel cell technology. Our objective is to spur more research in this area to develop fuel cell systems that approach the costs of inexpensive batteries for large-scale applications. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1727-1735, 2013

  16. Interfacial Behavior of Polymer Coated Nanoparticle

    NASA Astrophysics Data System (ADS)

    Qi, Luqing; Shamsijazeyi, Hadi; Mann, Jason; Verduzco, Rafael; Hirasaki, George; Rice University Team

    2015-03-01

    Oxidized carbon black (OCB) nanoparticle is functionalized with different coatings, i.e. alkyl group, polyvinyl alcohol (PVA) and partially sulfonated polyvinyl alcohol (sPVA). In oil and water systems, the functionalized nanoparticle is found to have a versatile dispersion i.e. in lower aqueous phase, in upper oil phase, or in middle phase microemulsion. Oil substitute n-octane and commercial oil IOSPAR have been test as oil phase; series of commercially available surfactant, C12-4,5 orthoxylene sulfonate(OXS), i-C13-(PO)7 -SO4Na (S13B), surfactant blend of anionic Alfoterra with nonionic Tergitol have been test as additive to help with the OCB dispersion. It is found that the OCB with sulfonated polyvinyl alcohol attachment (sPVA-OCB) stays in microemulsion; with the increase of salinity, it follows the microemulsion to go from lower phase, to middle phase, and to upper phase. The dispersion of sPVA and alkyl functionalized OCB (Cn-OCB-sPVA) is the balance of the length of alkyl and sPVA and the degree of sulfonation of PVA, depending on which, it can either disperse into microemulsion or form a separate layer. The sPVA-OCB also indicates a tolerance of high salinity; this is shown by the stable dispersion of it in blend surfactant solution of anionic Alfoterra and nonionic Tergitol at high salinity API brine(8% NaCl and 2% CaCl2). The study of different functionality on OCB dispersion can help design appropriate modified nanoparticle as additive for enhanced oil recovery either to reduce the interfacial tension between oil and water, or to stabilize microemulsion.

  17. Anion separation and preconcentration with cyclen and cyclen-resorcinarene derivatives.

    PubMed

    Wang, Jing; Harrison, Roger G; Lamb, John D

    2009-08-01

    N-undecyl cyclen and a resorcinarene bowl bearing four cyclen arms have been applied as anion exchangers in ion chromatography by strong adsorption to a reversed-phase column. The column loaded with the resorcinarene bowl cyclen tetramer exhibited significantly better performance in anion separation than that with N-undecyl cyclen monomer in isocratic elution mode. Both columns were tested for polarizable anion preconcentration or removal. By changing the eluent type from sodium bicarbonate to sodium hydroxide, the degree of protonation of the cyclen molecules could be modified, and the column capacity for anion retention adjusted thereby. Capacity gradient elution was successfully applied to removing sample matrix ions in the preconcentration of perchlorate and perrhenate ions as example analytes. PMID:19772718

  18. Synthesis and selective IR absorption properties of iminodiacetic-acid intercalated MgAl-layered double hydroxide

    SciTech Connect

    Wang Lijing; Xu Xiangyu; Evans, David G.; Duan Xue; Li Dianqing

    2010-05-15

    An MgAl-NO{sub 3}-layered double hydroxide (LDH) precursor has been prepared by a method involving separate nucleation and aging steps (SNAS). Reaction with iminodiacetic acid (IDA) under weakly acidic conditions led to the replacement of the interlayer nitrate anions by iminodiacetic acid anions. The product was characterized by XRD, FT-IR, TG-DTA, ICP, elemental analysis and SEM. The results show that the original interlayer nitrate anions of LDHs precursor were replaced by iminodiacetic acid anions and that the resulting intercalation product MgAl-IDA-LDH has an ordered crystalline structure. MgAl-IDA-LDH was mixed with low density polyethylene (LDPE) using a masterbatch method. LDPE films filled with MgAl-IDA-LDH showed a higher mid to far infrared absorption than films filled with MgAl-CO{sub 3}-LDH in the 7-25 {mu}m range, particularly in the key 9-11 {mu}m range required for application in agricultural plastic films. - Graphical abstract: Intercalation of iminodiacetic acid (IDA) anions in a MgAl-NO{sub 3}-layered double hydroxide host leads to an enhancement of its infrared absorbing ability for application in agricultural plastic films.

  19. Study of the structure and luminescent properties of terbium complex intercalated Zn/Al layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Gao, Xiaorui; Xie, Juan; Yin, Yaobing; Hao, Yongjing; Lian, Yiwei

    2016-01-01

    Terbium complex of ethylenediaminetetraacetate ([Tb(EDTA)]-) intercalated Zn/Al layered double hydroxide (LDH), as an inorganic-organic green-emitting phosphor, was synthesized through an ion exchange method. X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) spectra exhibit a successful intercalation of [Tb(EDTA)]- anions between the hydroxide sheets of the LDH. The basal spacing of 14.5 Å indicate a vertical arrangement of [Tb(EDTA)]- anions with the maximal dimension in the gallery is adopted. The luminescent properties of this material were studied by excitation and emission spectra. The results show that the strongest emission peak of Tb3+ ion occurs at 544 nm. This material may supply a candidate of green light emitting phosphor.

  20. Molecular dynamic simulations of iron (II) hydroxide in high temperature and supercritical water

    NASA Astrophysics Data System (ADS)

    Meng, Yuanliang

    In this study, the iron (II) hydroxide -- water system has been investigated at high temperatures by using molecular dynamics (MD) simulations. The simulation results reveal that at infinite dilution both Fe2+ cation and OH- anion have 6 water molecules within their first hydration shell and both types of ionic species experience a dramatic increase in their diffusion coefficients at near and supercritical conditions. The process of iron (II) hydroxide cluster formation has been simulated. The nano-clusters of larger sizes formed in supercritical water tend to be in an amorphous state. After having been quenched by an inert gas bath, iron (II) hydroxide nano-clusters with various structures have been produced. The geometries and associated binding energies of these species are given in detail. The vibrational spectra of iron (II) hydroxide clusters are also derived and compared with the spectrum of a bulk solid. The obtained results have a practical value for the analysis of potential corrosion products in supercritical water-cooled reactor (SCWR) which is employed in the new generation nuclear power plant design (GEN IV). This work also illustrates the process of hydrothermal synthesis of oxide nano-particles.

  1. Interfacial Composition of the Ionic Aqueous Solution Studied by the Adsorption of the Cationic Molecules

    NASA Astrophysics Data System (ADS)

    Song, Jinsuk; Kim, Mahn

    2009-03-01

    Knowing the interfacial composition of the ionic aqueous solution is important not only for understanding many atmospheric and environmental chemistry processes^1 but also for understanding many biological processes because the interaction between biomaterials happens often at the interfacial region such as water-vesicle interface in ionic aqueous solution. In this study, the surface anion density is estimated by measuring the surface density and adsorption angle of the cationic molecule, Malachite Green(MG) adsorbed at the air-ionic aqueous solution interface using the second harmonic generation technique. The anion number density at the interface increases with the increasing concentration of the ions and with the increasing size of the anions for spherical ions. It is consistent with other experimental measurements and simulation results^2,3. However, it seems that the anion density depends not only on the anion but also on the cation and shape and chemical composition of the ions. ^1 E. Knipping et al., Science 288, 301 (2000) ^2 S. Ghosal et al., Science 307, 563 (2005) ^3 P. Jungwirth et al., J. Phys. Chem. B 105, 10468 (2001)

  2. Charged Surfaces and Interfacial Ions.

    PubMed

    Kallay; Zalac

    2000-10-01

    Interfacial charge in a solid/liquid system is due to interactions of ions with surface sites affected by the electrostatic potential that is a consequence of their accumulation. The present theoretical approach is based on the so-called Surface Complexation Model that has several modifications known as either the 1-pK, the 2-pK, or the "MUSIC" model. These models assume different surface reactions and their equilibrium constants, taking into account electrostatic interactions. For that purpose the relationships between potentials affecting the state of interfacial ions and their surface densities need to be known, so that a certain model of the electrical interfacial layer should be introduced. The complexity of the problem results in the use of a variety of different theoretical approaches that cannot be distinguished experimentally. This article discusses several aspects of the problem, such as counterion association, structure of the electrical interfacial layer, potential-charge relationships, surface potentials, the zero charge condition, enthalpy of surface reactions, and the influence of the interfacial ionic equilibrium on the colloid stability. Copyright 2000 Academic Press. PMID:10998282

  3. Reactive oxygen species accelerate degradation of anion exchange membranes based on polyphenylene oxide in alkaline environments.

    PubMed

    Parrondo, Javier; Wang, Zhongyang; Jung, Min-Suk J; Ramani, Vijay

    2016-07-20

    Anion exchange membranes (AEM) based on polyphenylene oxide (PPO) suffered quaternary-ammonium-cation-site degradation in alkaline environments. Surprisingly, the degradation rate was considerably faster in the presence of molecular oxygen. We postulated that the AEM cation-site catalyzes the reduction of dioxygen by hydroxide ions to yield the superoxide anion radical and the highly reactive hydroxyl free radical. We substantiated our hypothesis by using a phosphorous-containing spin trap (5-diisopropoxy-phosphoryl-5-methyl-1-pyrroline-N-oxide) to detect the adducts for both free radicals in situ using (31)P-NMR spectroscopy. PMID:27381009

  4. New magnetic organic inorganic composites based on hydrotalcite-like anionic clays for drug delivery

    NASA Astrophysics Data System (ADS)

    Carja, Gabriela; Chiriac, Horia; Lupu, Nicoleta

    2007-04-01

    The structural "memory effect" of anionic clays was used to obtain layered double hydroxides (LDHs) with tailored magnetic properties, by loading iron oxides and/or spinel structures on iron partially substituted hydrotalcite-like materials. The obtained magnetic layered structures were further used as precursors for new hybrid nanostructures, such as aspirin-hydrotalcite-like anionic clays. Transmission electron microscopy (TEM) analysis shows that small iron oxide or spinel nanoparticles coexist with the fibrous drug particles on the surface of partially aggregated typical clay-like particles. The specific saturation magnetization of the loaded LDHs can be increased up to 70 emu/g by using specific post-synthesis treatments.

  5. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.

    1980-01-01

    The efforts on the synthesis of polymer anion redox membranes were mainly concentrated in two areas, membrane development and membrane fabrication. Membrane development covered the preparation and evaluation of experimental membranes systems with improved resistance stability and/or lower permeability. Membrane fabrication covered the laboratory scale production of prime candidate membranes in quantities of up to two hundred and sizes up to 18 inches x 18 inches (46 cm x 46 cm). These small (10 in x 11 in) and medium sized membranes were mainly for assembly into multicell units. Improvements in processing procedures and techniques for preparing such membrane sets lifted yields to over 90 percent.

  6. Interfacial tension of complex coacervated mussel adhesive protein according to the Hofmeister series.

    PubMed

    Lim, Seonghye; Moon, Dustin; Kim, Hyo Jeong; Seo, Jeong Hyun; Kang, In Seok; Cha, Hyung Joon

    2014-02-01

    Complex coacervation is a liquid-liquid phase separation in a colloidal system of two oppositely charged polyelectrolytes or colloids. The interfacial tension of the coacervate phase is the key parameter for micelle formation and interactions with the encapsulating material. However, the relationship between interfacial tensions and various salt solutions is poorly understood in complex coacervation. In the present work, the complex coacervate dynamics of recombinant mussel adhesive protein (MAP) with hyaluronic acid (HA) were determined in the presence of Hofmeister series salt ions. Using measurements of absorbance, hydrodynamic diameter, capillary force, and receding contact angle in the bulk phase, the interfacial tensions of complex coacervated MAP/HA were determined to be 0.236, 0.256, and 0.287 mN/m in 250 mM NaHCOO, NaCl, and NaNO3 solutions, respectively. The sequences of interfacial tensions and contact angles of the complex coacervates in the presence of three sodium salts with different anions were found to follow the Hofmeister ordering. The tendency of interfacial tension between the coacervate and dilute phases in the presence of different types of Hofmeister salt ions could provide a better understanding of Hofmeister effects on complex coacervated materials based on the protein-polysaccharide system. This information can also be utilized for microencapsulation and adsorption by controlling intramolecular interactions. In addition, the injection molding dynamics of mussel byssus formation was potentially explained based on the measured interfacial tension of coacervated MAP. PMID:24490867

  7. Cadmium-Aluminum Layered Double Hydroxide Microspheres for Photocatalytic CO2 Reduction.

    PubMed

    Saliba, Daniel; Ezzeddine, Alaa; Sougrat, Rachid; Khashab, Niveen M; Hmadeh, Mohamad; Al-Ghoul, Mazen

    2016-04-21

    We report the synthesis of cadmium-aluminum layered double hydroxide (CdAl LDH) using the reaction-diffusion framework. As the hydroxide anions diffuse into an agar gel matrix containing the mixture of aluminum and cadmium salts at a given ratio, they react to give the LDH. The LDH self-assembles inside the pores of the gel matrix into a unique spherical-porous shaped microstructure. The internal and external morphologies of the particles are studied by electron microscopy and tomography revealing interconnected channels and a high surface area. This material is shown to exhibit a promising performance in the photoreduction of carbon dioxide using solar light. Moreover, the palladium-decorated version shows a significant improvement in its reduction potential at room temperature. PMID:27028104

  8. Copper, silver, gold and zinc, cadmium, mercury oxides and hydroxides

    SciTech Connect

    Dirkse, T.P.

    1986-01-01

    This book provides a compilation of solubility data published up to 1984, including evaluations of the data. Data are presented on the following: copper (I) oxide; copper (II) oxide and hydroxide; silver (I) oxide; silver (II) oxide; gold (III) hydroxide; zinc oxide and hydroxide; cadmium oxide and hydroxide; and mercury (II) oxide.

  9. Fullerenols revisited as stable radical anions.

    PubMed

    Husebo, Lars O; Sitharaman, Balaji; Furukawa, Ko; Kato, Tatsuhisa; Wilson, Lon J

    2004-09-29

    The first exhaustive purification and characterization of the much-studied "fullerenols", prepared by reaction of C(60) in toluene with an oxygenated, aqueous NaOH solution using tetrabutylammonium hydroxide as a phase transfer catalyst, has been performed. The resulting fullerenol is not simply polyhydroxylated C(60) but rather is a structurally and electronically complex C(60) radical anion with a molecular formula of Na(+)(n)[C(60)O(x)(OH)(y)](n)(-) (where n = 2-3, x = 7-9, and y = 12-15) for three different, but identical, preparations. Surprisingly, Na(+)-fullerenol is paramagnetic, exhibiting mu(B) values in aqueous solution of 1.9-2.1 B.M. at 0.5 T and 300 K and R(1) proton relaxivities of 0.55-0.77 mM(-1)s(-1) at 20 MHz and 40 degrees C, values both slightly higher than those expected for a pure S = 1/2 spin system. ESR studies (ESE-FS and 2D nutation) of frozen aqueous solutions at 1.5 and 5.0 K establish that Na(+)-fullerenol is mainly S = 1/2 with a minor, but significant, component of S = 1. Thus, this is the first report to characterize these widely studied, water-soluble fullerenols as stable radical anions. The stability of the S = 1/2 Na(+)-fullerenol radical is likely due to a highly derivatized C(60) surface that protects a cyclopentadienyl radical center on the fullerene. PMID:15382940

  10. 21 CFR 184.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Specific Substances Affirmed as GRAS § 184.1428 Magnesium hydroxide. (a) Magnesium hydroxide (Mg(OH)2, CAS... Chemicals Codex, 3d Ed. (1981), p. 178, which is incorporated by reference. Copies are available from the... § 170.3(o)(20) of this chapter; a pH control agent as defined in § 170.3(o)(23) of this chapter; and...

  11. Pseudorotation in fullerene anions

    NASA Astrophysics Data System (ADS)

    Dunn, Janette L.; Hands, Ian D.; Bates, Colin A.

    2007-07-01

    Jahn-Teller (JT) problems are often characterised by an adiabatic potential energy surface (APES) containing either a set of isoenergetic wells or a trough of equivalent-energy points, which may be warped by higher-order coupling terms or anisotropic effects. In all three cases, the JT effect will be dynamic. Either tunnelling between the wells or rotation (of a distortion) around the trough will restore the original symmetry of the system. This motion is referred to as pseudorotation. It should be possible to observe a JT system in a distorted geometry if measurements are made on a sufficiently short timescale. In various cubic systems, this timescale has been calculated to be the order of picoseconds. Such timescales are accessible using modern methods of ultrafast spectroscopy. Measurements of pseudorotation rates can lead to important information on the strength and nature of the JT coupling present. We will present analytical calculations that allow the rate of pseudorotation to be determined in terms of the vibronic coupling parameters. We will show how these results can be applied to E ⊗ e systems and then to the more complicated system applicable to C60- anions. This is of particular interest because of the high icosahedral symmetry of fullerene ions and also because of the many potential uses of materials containing these ions. We conclude by outlining experiments that should be capable of measuring pseudorotation in C 60 anions.

  12. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.

    1982-01-01

    The synthesis and fabrication of polymeric anion permselective membranes for redox systems are discussed. Variations of the prime candidate anion membrane formulation to achieve better resistance and/or lower permeability were explored. Processing parameters were evaluated to lower cost and fabricate larger sizes. The processing techniques to produce more membranes per batch were successfully integrated with the fabrication of larger membranes. Membranes of about 107 cm x 51 cm were made in excellent yield. Several measurements were made on the larger sample membranes. Among the data developed were water transport and transference numbers for these prime candidate membranes at 20 C. Other work done on this system included characterization of a number of specimens of candidate membranes which had been returned after service lives of up to sixteen months. Work with new polymer constituents, with new N.P.'s, catalysts and backing fabrics is discussed. Some work was also done to evaluate other proportions of the ingredients of the prime candidate system. The adoption of a flow selectivity test at elevated temperature was explored.

  13. Understanding Regeneration of Arsenate-Loaded Ferric Hydroxide-Based Adsorbents

    PubMed Central

    Chaudhary, Binod Kumar; Farrell, James

    2015-01-01

    Abstract Adsorbents comprising ferric hydroxide loaded on a variety of support materials are commonly used to remove arsenic from potable water. Although several studies have investigated the effects of support properties on arsenic adsorption, there have been no investigations of their effects on adsorbent regeneration. Furthermore, the effect of regenerant solution composition and the kinetics of regeneration have not been investigated. This research investigated the effects of adsorbent and regenerant solution properties on the kinetics and efficiency of regeneration of arsenate-loaded ferric hydroxide-based adsorbents. Solutions containing only 0.10–5.0 M NaOH or 0.10–1.0 M NaCl, as well as solutions containing both compounds, were used as regenerants. On all media, >99% of arsenate was adsorbed through complexation with ferric hydroxide. Arsenate recovery was controlled by both equilibrium and kinetic limitations. Adsorbents containing support material with weak base anion-exchange functionality or no anion-exchange functionality could be regenerated with NaOH solutions alone. Regeneration of media containing strong base anion (SBA)-exchange functionality was greatly enhanced by addition of 0.10 M NaCl to the NaOH regenerant solutions. Adsorbed silica had a significant effect on NaOH regeneration of media containing type I SBA-exchange functionality, but on other media, adsorbed silica had little impact on regeneration. On all media, 5–25% of arsenate was resistant to desorption in 1.0 M NaOH solutions. However, the use of 2.5–5.0 M NaOH solutions significantly reduced the desorption-resistant fraction. PMID:25873779

  14. Dynamic chemistry of anion recognition

    SciTech Connect

    Custelcean, Radu

    2012-01-01

    In the past 40 years, anion recognition by synthetic receptors has grown into a rich and vibrant research topic, developing into a distinct branch of Supramolecular Chemistry. Traditional anion receptors comprise organic scaffolds functionalized with complementary binding groups that are assembled by multistep organic synthesis. Recently, a new approach to anion receptors has emerged, in which the host is dynamically self-assembled in the presence of the anionic guest, via reversible bond formation between functional building units. While coordination bonds were initially employed for the self-assembly of the anion hosts, more recent studies demonstrated that reversible covalent bonds can serve the same purpose. In both cases, due to their labile connections, the molecular constituents have the ability to assemble, dissociate, and recombine continuously, thereby creating a dynamic combinatorial library (DCL) of receptors. The anionic guests, through specific molecular recognition, may then amplify (express) the formation of a particular structure among all possible combinations (real or virtual) by shifting the equilibria involved towards the most optimal receptor. This approach is not limited to solution self-assembly, but is equally applicable to crystallization, where the fittest anion-binding crystal may be selected. Finally, the pros and cons of employing dynamic combinatorial chemistry (DCC) vs molecular design for developing anion receptors, and the implications of both approaches to selective anion separations, will be discussed.

  15. Mass spectrometry of interfacial layers during fast aqueous aerosol/ozone gas reactions of atmospheric interest

    NASA Astrophysics Data System (ADS)

    Enami, S.; Vecitis, C. D.; Cheng, J.; Hoffmann, M. R.; Colussi, A. J.

    2008-04-01

    The oxidations of sulfite and iodide in the interfacial layers of aqueous microdroplets exposed to O 3(g) for 1 ms are investigated by online mass spectrometry of the electrostatically ejected anions. S(IV) oxidation losses in Na 2SO 3 microdroplets are proportional to [S(IV)] [O 3(g)] up to ˜90% conversion. I - is more abundant than HSO3- in the interfacial layers of equimolar (Na 2SO 3 + NaI) microdroplets and ˜3 times more reactive than HSO3- toward O 3(aq) in bulk solution, but it is converted withminimalloss to I3- and IO3- plus a persistent ISO3- intermediate. These observations reveal unanticipated interfacial gradients, reactivity patterns and transport phenomena that had not been taken into account in previous treatments of fast gas-liquid reactions.

  16. Mössbauer and XRD study of intercalated CaFe-layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Sipiczki, Mónika; Kuzmann, Ernő; Pálinkó, István; Homonnay, Zoltán; Sipos, Pál; Kukovecz, Ákos; Kónya, Zoltán

    2014-04-01

    N-containing fully saturated (L-prolinate) or aromatic (indole-2-carboxylate) heterocyclic anions were immobilised in CaFe-layered double hydroxide with the dehydration-rehydration method from aqueous ethanol or acetone. The structure of the resulting organic-inorganic hybrids was characterised mainly with powder X-ray diffraction and 57Fe Mössbauer spectroscopy, and as supplementary analysis scanning electron microscopy, energy dispersive X-ray spectroscopy with elemental mapping and molecular modelling were also applied. It was found that the solvent mixture used for the synthesis caused enormous difference in the interlayer spacings of the obtained inorganic-organic hybrids.

  17. Interfacial rheology in complex flow

    NASA Astrophysics Data System (ADS)

    Martin, Jeffrey; Hudson, Steven

    2009-03-01

    Multiphase liquid systems are omnipresent in and essential to everyday life, e.g. foods, pharmaceutics, cosmetics, paints, oil recovery, etc. The morphology and stability of such systems depend on dynamic interfacial properties and processes. Typical methods utilized to measure such interfacial properties often employ drops that are much larger and flows that are much simpler than those encountered in typical processing applications. A microfluidic approach is utilized to measure dynamic structure and kinetics in multiphase systems with drop sizes comparable to those encountered in applications and flow complexity that is easily adjustable. The internal circulation and deformation of an aqueous droplet in clear mineral oil is measured using particle tracers and a detailed shape analysis, which is capable of measuring sub-micron deviations in drop shape. Deformation dynamics, detailed drop shape, interfacial tension, and internal circulation patterns and velocities are measured in Poiseuille and transient elongational flows. Flow kinematics are adjusted by varying the microchannel geometry, relative drop size, and drop height. The effects of confinement on interfacial dynamics and circulation patterns and velocities are also explored.

  18. Surface modification of magnesium hydroxide using vinyltriethoxysilane by dry process

    NASA Astrophysics Data System (ADS)

    Lan, Shengjie; Li, Lijuan; Xu, Defang; Zhu, Donghai; Liu, Zhiqi; Nie, Feng

    2016-09-01

    In order to improve the compatibility between magnesium hydroxide (MH) and polymer matrix, the surface of MH was modified using vinyltriethoxysilane (VTES) by dry process and the interfacial interaction between MH and VTES was also studied. Zeta potential measurements implied that the MH particles had better dispersion and less aggregation after modification. Sedimentation tests showed that the surface of MH was transformed from hydrophilic to hydrophobic, and the dispersibility and the compatibility of MH particles significantly improved in the organic phase. Scanning electronic microscopy (SEM), Transmission electron microscopy (TEM) and X-ray powder diffraction (XRD) analyses showed that a thin layer had formed on the surface of the modified MH, but did not alter the material's crystalline phase. Fourier transform infrared (FT-IR) spectra, X-ray photoelectron spectra (XPS) and Thermogravimetric analysis (TGA) showed that the VTES molecules bound strongly to the surface of MH after modification. Chemical bonds (Sisbnd Osbnd Mg) formed by the reaction between Si-OC2H5 and hydroxyl group of MH, also there have physical adsorption effect in the interface simultaneously. A modification mechanism of VTES on the MH surface by dry process was proposed, which different from the modification mechanism by wet process.

  19. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Alexander, S.; Hodgdon, R. B.

    1977-01-01

    The objective of NAS 3-20108 was the development and evaluation of improved anion selective membranes useful as efficient separators in a redox power storage cell system being constructed. The program was divided into three parts, (a) optimization of the selected candidate membrane systems, (b) investigation of alternative membrane/polymer systems, and (c) characterization of candidate membranes. The major synthesis effort was aimed at improving and optimizing as far as possible each candidate system with respect to three critical membrane properties essential for good redox cell performance. Substantial improvements were made in 5 candidate membrane systems. The critical synthesis variables of cross-link density, monomer ratio, and solvent composition were examined over a wide range. In addition, eight alternative polymer systems were investigated, two of which attained candidate status. Three other alternatives showed potential but required further research and development. Each candidate system was optimized for selectivity.

  20. Organic Anion Transporting Polypeptides

    PubMed Central

    Stieger, Bruno; Hagenbuch, Bruno

    2013-01-01

    Organic anion transporting polypeptides or OATPs are central transporters in the disposition of drugs and other xenobiotics. In addition, they mediate transport of a wide variety of endogenous substrates. The critical role of OATPs in drug disposition has spurred research both in academia and in the pharmaceutical industry. Translational aspects with clinical questions are the focus in academia, while the pharmaceutical industry tries to define and understand the role these transporters play in pharmacotherapy. The present overview summarizes our knowledge on the interaction of food constituents with OATPs, and on the OATP transport mechanisms. Further, it gives an update on the available information on the structure-function relationship of the OATPs, and finally, covers the transcriptional and posttranscriptional regulation of OATPs. PMID:24745984

  1. THE KINETICS OF SAPONIFICATION OF IODOACETIC ACID BY SODIUM HYDROXIDE AND BY CERTAIN ALKALINE BUFFER SOLUTIONS.

    PubMed

    Brdicka, R

    1936-07-20

    1. The rate of the saponification of iodoacetic acid in sodium hydroxide and alkaline buffer solutions yielding glycollic acid was measured by means of Heyrovský's polarographic method. 2. From the bimolecular velocity constants, increasing with the ionic strength of the solution, the Brönsted factor, F, which characterizes the primary salt effect, was calculated. 3. In the borate buffer solutions the monomolecular constants of the saponification were determined which, at values above the pH of neutralization of boric acid, show a proportionality to the concentration of hydroxyl anions. Below the pH of neutralization of boric acid, they are proportional to the concentration of borate anions.

  2. New layered double hydroxides by prepared by the intercalation of gibbsite

    NASA Astrophysics Data System (ADS)

    Rees, Jennifer R.; Burden, Chloe S.; Fogg, Andrew M.

    2015-04-01

    New layered double hydroxides (LDHs) with the composition [MAl4(OH)12]Cl2·1.5H2O (M=Co, Ni) have been prepared by reacting gibbsite, γ-Al(OH)3, with the appropriate chloride salt in a synthesis in which the water of crystallization is the only solvent present and fully characterized. These LDHs have been shown to undergo facile anion exchange reactions with both organic and inorganic anions at room temperature making them comparable to other LDHs in this respect. Reactions under the same conditions with CuCl2·2H2O and ZnCl2 failed to form the desired LDHs but those with nitrate salts did lead to the formation of the previously reported [MAl4(OH)12](NO3)2·1.5H2O (M=Co, Ni) compounds.

  3. Synthesis and photoluminescence of red emitting phosphors of europium complex intercalated layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Gao, Xiaorui; Gao, Zhen; Yin, Xiaoru; Xie, Juan

    2015-12-01

    An inorganic-organic red emitting phosphor, europium ethylenediaminetetraacetate complex ([Eu(EDTA)]-) anions intercalated Mg/Al and Zn/Al layered double hydroxides (LDHs) were synthesized through an ion exchange method. X-ray powder diffraction (XRD) results exhibit that a nearly vertical arrangement of [Eu(EDTA)]- anions with the maximal dimension in the gallery is adopted. Measurement of the excitation and emission spectra show that the two materials display high red luminescence from Eu3+ ions. Furthermore, Mg/Al LDH containing europium complex has higher luminescence intensity than Zn/Al LDH, which probably was related with more inversion asymmetry sites of Eu3+ occurring in the Mg/Al LDH.

  4. Layered double hydroxide-based nanomaterials as highly efficient catalysts and adsorbents.

    PubMed

    Li, Changming; Wei, Min; Evans, David G; Duan, Xue

    2014-11-01

    Layered double hydroxides (LDHs) are a class of anion clays consisting of brucite-like host layers and interlayer anions, which have attracted increasing interest in the fields of catalysis/adsorption. By virtue of the versatility in composition, morphology, and architecture of LDH materials, as well as their unique structural properties (intercalation, topological transformation, and self-assembly with other functional materials), LDHs display great potential in the design and fabrication of nanomaterials applied in photocatalysis, heterogeneous catalysis, and adsorption/separation processes. Taking advantage of the structural merits and various control synthesis strategies of LDHs, the active center structure (e.g., crystal facets, defects, geometric and electronic states, etc.) and macro-nano morphology can be facilely manipulated for specific catalytic/adsorbent processes with largely enhanced performances. In this review, the latest advancements in the design and preparation of LDH-based functional nanomaterials for sustainable development in catalysis and adsorption are summarized.

  5. Interfacial behavior of polymer electrolytes

    SciTech Connect

    Kerr, John; Kerr, John B.; Han, Yong Bong; Liu, Gao; Reeder, Craig; Xie, Jiangbing; Sun, Xiaoguang

    2003-06-03

    Evidence is presented concerning the effect of surfaces on the segmental motion of PEO-based polymer electrolytes in lithium batteries. For dry systems with no moisture the effect of surfaces of nano-particle fillers is to inhibit the segmental motion and to reduce the lithium ion transport. These effects also occur at the surfaces in composite electrodes that contain considerable quantities of carbon black nano-particles for electronic connection. The problem of reduced polymer mobility is compounded by the generation of salt concentration gradients within the composite electrode. Highly concentrated polymer electrolytes have reduced transport properties due to the increased ionic cross-linking. Combined with the interfacial interactions this leads to the generation of low mobility electrolyte layers within the electrode and to loss of capacity and power capability. It is shown that even with planar lithium metal electrodes the concentration gradients can significantly impact the interfacial impedance. The interfacial impedance of lithium/PEO-LiTFSI cells varies depending upon the time elapsed since current was turned off after polarization. The behavior is consistent with relaxation of the salt concentration gradients and indicates that a portion of the interfacial impedance usually attributed to the SEI layer is due to concentrated salt solutions next to the electrode surfaces that are very resistive. These resistive layers may undergo actual phase changes in a non-uniform manner and the possible role of the reduced mobility polymer layers in dendrite initiation and growth is also explored. It is concluded that PEO and ethylene oxide-based polymers are less than ideal with respect to this interfacial behavior.

  6. Resonant spectra of quadrupolar anions

    NASA Astrophysics Data System (ADS)

    Fossez, K.; Mao, Xingze; Nazarewicz, W.; Michel, N.; Garrett, W. R.; Płoszajczak, M.

    2016-09-01

    In quadrupole-bound anions, an extra electron is attached at a sufficiently large quadrupole moment of a neutral molecule, which is lacking a permanent dipole moment. The nature of the bound states and low-lying resonances of such anions is of interest for understanding the threshold behavior of open quantum systems in general. In this work, we investigate the properties of quadrupolar anions as halo systems, the formation of rotational bands, and the transition from a subcritical to supercritical electric quadrupole moment. We solve the electron-plus-rotor problem using a nonadiabatic coupled-channel formalism by employing the Berggren ensemble, which explicitly contains bound states, narrow resonances, and the scattering continuum. The rotor is treated as a linear triad of point charges with zero monopole and dipole moments and nonzero quadrupole moment. We demonstrate that binding energies and radii of quadrupolar anions strictly follow the scaling laws for two-body halo systems. Contrary to the case of dipolar anions, ground-state band of quadrupolar anions smoothly extend into the continuum, and many rotational bands could be identified above the detachment threshold. We study the evolution of a bound state of an anion as it dives into the continuum at a critical quadrupole moment and we show that the associated critical exponent is α =2 . Everything considered, quadrupolar anions represent a perfect laboratory for the studies of marginally bound open quantum systems.

  7. Synthesis, characterization, and controlled release anticorrosion behavior of benzoate intercalated Zn-Al layered double hydroxides

    SciTech Connect

    Wang, Yi; Zhang, Dun

    2011-11-15

    Graphical abstract: The benzoate anion released from Zn-Al LDHs provides a more effective long-term protection against corrosion of Q235 carbon steel in 3.5% NaCl solution. Highlights: {yields} A benzoate anion corrosion inhibitor intercalated Zn-Al layered double hydroxides (LDHs) has been assembled by coprecipitation method. {yields} The kinetic simulation indicates that the ion-exchange one is responsible for the release process and the diffusion through particle is the rate limiting step. {yields} A significant reduction of the corrosion rate is observed when the LDH nanohybrid is present in the corrosive media. -- Abstract: Corrosion inhibitor-inorganic clay composite including benzoate anion intercalated Zn-Al layered double hydroxides (LDHs) are assembled by coprecipitation. Powder X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectrum analyses indicate that the benzoate anion is successfully intercalated into the LDH interlayer and the benzene planes are vertically bilayer-positioned as a quasi-guest ion-pair form in the gallery space. Kinetic simulation for the release data, XRD and FT-IR analyses of samples recovered from the release medium indicate that ion-exchange is responsible for the release process and diffusion through the particle is also indicated to be the rate-limiting step. The anticorrosion capabilities of LDHs loaded with corrosion inhibitor toward Q235 carbon steel are analyzed by polarization curve and electrochemical impedance spectroscopy methods. Significant reduction of corrosion rate is observed when the LDH nanohybrid is present in the corrosive medium. This hybrid material may potentially be applied as a nanocontainer in self-healing coatings.

  8. Anion-exchange nanospheres as titration reagents for anionic analytes.

    PubMed

    Zhai, Jingying; Xie, Xiaojiang; Bakker, Eric

    2015-08-18

    We present here anion-exchange nanospheres as novel titration reagents for anions. The nanospheres contain a lipophilic cation for which the counterion is initially Cl(-). Ion exchange takes place between Cl(-) in the nanospheres and a more lipophilic anion in the sample, such as ClO4(-) and NO3(-). Consecutive titration in the same sample solution for ClO4(-) and NO3(-) were demonstrated. As an application, the concentration of NO3(-) in spinach was successfully determined using this method.

  9. Insights into the behaviour of biomolecules on the early Earth: The concentration of aspartate by layered double hydroxide minerals

    NASA Astrophysics Data System (ADS)

    Grégoire, Brian; Erastova, Valentina; Geatches, Dawn L.; Clark, Stewart J.; Greenwell, H. Christopher; Fraser, Donald G.

    2016-03-01

    The role of mineral surfaces in concentrating and facilitating the polymerisation of simple protobiomolecules during the Hadean and Archean has been the subject of much research in order to constrain the conditions that may have led to the origin of life on early Earth. Here we examine the adsorption of the amino acid aspartate on layered double hydroxide minerals, and use a combined computer simulation - experimental spectroscopy approach to gain insight into the resulting structures of the host-aspartate material. We show that the uptake of aspartate occurs in alkaline solution by anion exchange of the dianion form of aspartate, rather than by surface adsorption. Anion exchange only occurs at values of pH where a significant population of aspartate has the amino group deprotonated, and is then highly efficient up to the mineral anion exchange capacity.

  10. Interlayer interaction in Ca-Fe layered double hydroxides intercalated with nitrate and chloride species

    NASA Astrophysics Data System (ADS)

    Al-Jaberi, Muayad; Naille, Sébastien; Dossot, Manuel; Ruby, Christian

    2015-12-01

    Ca-Fe layered double hydroxide (LDH) intercalated with chloride and nitrate ions has been synthesized with varying CaII:FeIII molar ratios of the initial solution. Phase pure LDH is observed with CaII:FeIII molar ratio of 2:1 and a mixture of LDH and Ca(OH)2 is formed for CaII:FeIII molar ratios higher than 2:1. Vibrational spectroscopies (Raman and IR) were used successfully to understand the interaction between the cationic and anionic sheets. The Raman bands positions at lower frequencies (150-600 cm-1) are intimately correlated to the nature of the divalent and trivalent ions but also to the nature of the anions. Indeed, a shift of ˜9 cm-1 is observed for the Raman double bands situated in the 300-400 cm-1 region when comparing Raman spectra of CaFe-LDH containing either nitrate or chloride ions. Two types of nitrate environments are observed namely free (non-hydrogen bonded) nitrate and nitrate hydrogen bonded to the interlayer water or to the 'brucite-like' hydroxyl surface. Multiple types of water structure are observed and would result from different hydrogen bond structures. Water bending modes are identified at 1645 cm-1 greater than the one observed for LDH intercalated with chloride anions (1618 cm-1), indicating that the water is strongly hydrogen bonded to the nitrate anions.

  11. Iodine Sequestration Using Delafossites and Layered Hydroxides

    SciTech Connect

    J.D. Pless; J.B. Chwirka; J.L. Krumhansl

    2006-03-28

    The objective of this document is to report on early success for sequestering {sup 129}I. Sorption coefficients (K{sub d}) for I{sup -} and IO{sub 3}{sup -} onto delafossites, spinels and layered metal hydroxides were measured in order to compare their applicability for sequestering {sup 129}I. The studies were performed using a dilute fluid composition representative of groundwater indigenous to the Yucca mountain area. Delafossites generally exhibited relatively poor sorption coefficients (< 10{sup 1.7} mL/g). In contrast, the composition of the layered hydroxides significantly affects their ability to sorb I. Cu/Al and Cu/Cr layered hydroxide samples exhibit K{sub d}'s greater than 10{sup 3} mL/g for both I{sup -} and IO{sub 3}{sup -}.

  12. Ion specific effects on the stability of layered double hydroxide colloids.

    PubMed

    Pavlovic, Marko; Huber, Robin; Adok-Sipiczki, Monika; Nardin, Corinne; Szilagyi, Istvan

    2016-05-01

    Positively charged layered double hydroxide particles composed of Mg(2+) and Al(3+) layer-forming cations and NO3(-) charge compensating anions (MgAl-NO3-LDH) were synthesized and the colloidal stability of their aqueous suspensions was investigated in the presence of inorganic anions of different charges. The formation of the layered structure was confirmed by X-ray diffraction, while the charging and aggregation properties were explored by electrophoresis and light scattering. The monovalent anions adsorb on the oppositely charged surface to a different extent according to their hydration state leading to the Cl(-) > NO3(-) > SCN(-) > HCO3(-) order in surface charge densities. The ions on the right side of the series induce the aggregation of MgAl-NO3-LDH particles at lower concentrations, whereas in the presence of the left ones, the suspensions are stable even at higher salt levels. The adsorption of multivalent anions gave rise to charge neutralization and charge reversal at appropriate concentrations. For some di, tri and tetravalent ions, charge reversal resulted in restabilization of the suspensions in the intermediate salt concentration regime. Stable samples were also observed at low salt levels. Particle aggregation was fast near the charge neutralization point and at high concentrations. These results, which evidence the colloidal stability of MgAl-NO3-LDH in the presence of various anions, are of prime fundamental interest. These are also critical for applications to develop stable suspensions of primary particles for water purification processes, with the aim of the removal of similar anions by ion exchange. PMID:26997621

  13. Interfacial Chemistry of Aqueous Sulfur/Iodide Aerosol Microdroplets in Gaseous Ozone

    NASA Astrophysics Data System (ADS)

    Enami, S.; Vecitis, C. D.; Cheng, J.; Colussi, A. J.; Hoffmann, M. R.

    2007-12-01

    The intermediates ISO3- (m/z = 207) and IS2O3- (m/z = 239) generated in aqueous (iodide - thiosulfate) microdroplets traversing dilute ozone gas plumes at atmospheric pressure are detected via online electrospray mass spectrometry within 1 ms, and their stabilities gauged by collision-induced dissociation. The simultaneous detection of anionic reactants and the S2O62-, HSO4-, IO3- and I3- products as a function of experimental conditions provides evidence of unique interfacial reaction kinetics. Although ozone reacts ~3-4 times faster with I- than S2O332- in bulk solution, only S2O32- is apparently oxidized in [I--]o/[S2O32- ]o = 10 microdroplets below [O3(g)] ~ 50 ppm. The sulfite to sulfate and iodide to triiodide and iodate oxidations in the interfacial layers of aqueous thiosulfate or mixed thiosulfate and iodide microdroplets briefly exposed to dilute O3(g) gas mixtures are also investigated. S(IV) oxidation kinetics in sodium thiosulfate solutions, where the rates are proportional to [S(IV)] [O3(g)] in the ranges investigated, correspond to a surface-specific reaction. I3-/IO3- yields based on interfacial I- losses exceed their stoichiometric limits in the presence of excess S(IV), revealing that interfacial I- is competitively replenished from the microdroplets inner layers. Present results provide unequivocal evidence of distinct interfacial chemistry in gas-aerosol reactions of atmospheric relevance.

  14. Anion transport with halogen bonds.

    PubMed

    Jentzsch, Andreas Vargas; Matile, Stefan

    2015-01-01

    This review covers the application of halogen bonds to transport anions across lipid bilayer membranes. The introduction provides a brief description of biological and synthetic transport systems. Emphasis is on examples that explore interactions beyond the coordination with lone pairs or hydrogen bonds for the recognition of cations and anions, particularly cation-π and anion-π interactions, and on structural motifs that are relevant for transport studies with halogen bonds. Section 2 summarizes the use of macrocyclic scaffolds to achieve transport with halogen bonds, focusing on cyclic arrays of halogen-bond donors of different strengths on top of calixarene scaffolds. This section also introduces methods to study anion binding in solution and anion transport in fluorogenic vesicles. In Sect. 3, transport studies with monomeric halogen bond-donors are summarized. This includes the smallest possible organic anion transporter, trifluoroiodomethane, a gas that can be bubbled through a suspension of vesicles to turn on transport. Anion transport with a gas nicely illustrates the power of halogen bonds for anion transport. Like hydrogen bonds, they are directional and strong, but compared to hydrogen-bond donors, halogen-bond donors are more lipophilic. Section 3 also offers a concise introduction to the measurement of ion selectivity in fluorogenic vesicles and conductance experiments in planar bilayer membranes. Section 4 introduces the formal unrolling of cyclic scaffolds into linear scaffolds that can span lipid bilayers. As privileged transmembrane scaffolds, the importance of hydrophobically matching fluorescent p-oligophenyl rods is fully confirmed. The first formal synthetic ion channel that operates by cooperative multiion hopping along transmembrane halogen-bonding cascades is described. Compared to homologs for anion-π interactions, transport with halogen bonds is clearly more powerful.

  15. Supramolecular interfacial architectures for biosensing

    NASA Astrophysics Data System (ADS)

    Yu, Fang; Yao, Danfeng; Christensen, Danica; Neumann, Thomas; Sinner, Eva-Kathrin; Knoll, Wolfgang

    2004-12-01

    This contribution summarizes some of our efforts in designing, assembling and functionally characterizing supramolecular interfacial architectures for bio-affinity studies and for biosensor development. All the surface interaction studies will be based on the recently introduced novel sensor platforms involving surface plasmon fluorescence spectroscopy (SPFS) and -microscopy (SPFM). Emphasis will be put on documenting the distance-dependence of fluorescence intensity at the metal-dielectric interface and utilizing this principle to optimize the conformation/orientation of the interfacial supra-molecular sensor coatings. This is exemplified by a number of examples, including a layer-by-layer assembly system, antibody-antigen interactions, oligonucleotide-oligonucleotide, and oligonucleotide-PCR amplicon hybridization. For practical sensing purposes, a three-dimensionally extended surface coating is then employed to overcome the fluorescence quenching problem on a planar matrix. A commercial dextran layer is shown to be an optimized matrix for SPFS, with an example of a protein-binding study.

  16. Mechanics of interfacial composite materials.

    PubMed

    Subramaniam, Anand Bala; Abkarian, Manouk; Mahadevan, L; Stone, Howard A

    2006-11-21

    Recent experiments and simulations have demonstrated that particle-covered fluid/fluid interfaces can exist in stable nonspherical shapes as a result of the steric jamming of the interfacially trapped particles. The jamming confers the interface with solidlike properties. We provide an experimental and theoretical characterization of the mechanical properties of these armored objects, with attention given to the two-dimensional granular state of the interface. Small inhomogeneous stresses produce a plastic response, while homogeneous stresses produce a weak elastic response. Shear-driven particle-scale rearrangements explain the basic threshold needed to obtain the near-perfect plastic deformation that is observed. Furthermore, the inhomogeneous stress state of the interface is exhibited experimentally by using surfactants to destabilize the particles on the surface. Since the interfacially trapped particles retain their individual characteristics, armored interfaces can be recognized as a kind of composite material with distinct chemical, structural, and mechanical properties.

  17. Quaternized poly (styrene-co-vinylbenzyl chloride) anion exchange membranes for alkaline water electrolysers

    NASA Astrophysics Data System (ADS)

    Vengatesan, S.; Santhi, S.; Jeevanantham, S.; Sozhan, G.

    2015-06-01

    In this study, poly (ST-co-VBC) based anion exchange membranes with different styrene to VBC ratios (1: 0.16, 1: 0.33 and 1: 1) have been prepared via chloromethylation-free synthetic route using aromatic vinyl monomers. The synthesized co-polymers are identified by FTIR and 1H-NMR analysis. Hydroxide (OH-) ion conductivity of the anion exchange membrane with styrene to VBC ratio of 1: 0.33 is as high as 6.8 × 10-3 S cm-1 in de-ionised water at 25 °C. The membrane also acquires the ion-exchange capacity of 2.14 meq. g-1, and the water uptake of 127%. Membrane-electrode-assembly (MEA) using the anion exchange membrane and Ni - foam catalyst demonstrate the current density of 40 mA cm-2 at 2.3 V in a water electrolyser cell.

  18. Anionic ring-opening polymerization of beta-alkoxymethyl-substituted beta-lactones.

    PubMed

    Adamus, Grazyna; Kowalczuk, Marek

    2008-02-01

    We report on anionic ring-opening polymerization (ROP) of racemic beta-(methoxymethyl)-beta-propiolactone (MOMPL) and beta-(ethoxymethyl)-beta-propiolactone (EOMPL) initiated by supramolecular complex of potassium acetate and tetrabutylammonium acetate (Bu4N+ Ac) as well as by tetrabutylammonium hydroxide, respectively. Structure of the resulting polymers has been established at the molecular level by electrospray ionization multistage mass spectrometry (ESI-MS(n)) and has been confirmed by FT-IR, NMR, and GPC analyses. Similar behavior of MOMPL and EOMPL with respect to already-studied beta-alkyl-substituted beta-lactones, e.g., beta-butyrolactone (MPL), has been observed under the conditions of anionic ROP (including observed side reactions leading to unsaturated end groups) and the already-established mechanisms of anionic polymerization of beta-alkyl-substituted beta-lactones are extended on beta-alkoxymethyl-substituted ones. PMID:18179174

  19. Method of manufacturing positive nickel hydroxide electrodes

    DOEpatents

    Gutjahr, M.A.; Schmid, R.; Beccu, K.D.

    1975-12-16

    A method of manufacturing a positive nickel hydroxide electrode is discussed. A highly porous core structure of organic material having a fibrous or reticular texture is uniformly coated with nickel powder and then subjected to a thermal treatment which provides sintering of the powder coating and removal of the organic core material. A consolidated, porous nickel support structure is thus produced which has substantially the same texture and porosity as the initial core structure. To provide the positive electrode including the active mass, nickel hydroxide is deposited in the pores of the nickel support structure.

  20. Defluoridation from aqueous solutions by granular ferric hydroxide (GFH).

    PubMed

    Kumar, Eva; Bhatnagar, Amit; Ji, Minkyu; Jung, Woosik; Lee, Sang-Hun; Kim, Sun-Joon; Lee, Giehyeon; Song, Hocheol; Choi, Jae-Young; Yang, Jung-Seok; Jeon, Byong-Hun

    2009-02-01

    This research was undertaken to evaluate the feasibility of granular ferric hydroxide (GFH) for fluoride removal from aqueous solutions. Batch experiments were performed to study the influence of various experimental parameters such as contact time (1 min-24h), initial fluoride concentration (1-100 mgL(-1)), temperature (10 and 25 degrees C), pH (3-12) and the presence of competing anions on the adsorption of fluoride on GFH. Kinetic data revealed that the uptake rate of fluoride was rapid in the beginning and 95% adsorption was completed within 10 min and equilibrium was achieved within 60 min. The sorption process was well explained with pseudo-first-order and pore diffusion models. The maximum adsorption capacity of GFH for fluoride removal was 7.0 mgg(-1). The adsorption was found to be an endothermic process and data conform to Langmuir model. The optimum fluoride removal was observed between pH ranges of 4-8. The fluoride adsorption was decreased in the presence of phosphate followed by carbonate and sulphate. Results from this study demonstrated potential utility of GFH that could be developed into a viable technology for fluoride removal from drinking water.

  1. Enhancement of the coercivity in Co-Ni layered double hydroxides by increasing basal spacing.

    PubMed

    Zhang, Cuijuan; Tsuboi, Tomoya; Namba, Hiroaki; Einaga, Yasuaki; Yamamoto, Takashi

    2016-09-14

    The magnetic properties of layered double hydroxides (LDH) containing transition metal ions can still develop, compared with layered metal hydroxide salts which exhibit structure-dependent magnetism. In this article, we report the preparation of a hybrid magnet composed of Co-Ni LDH and n-alkylsulfonate anions (Co-Ni-CnSO3 LDH). As Co-Ni LDH is anion-exchangeable, we can systematically control the interlayer spacing by intercalating n-alkylsulfonates with different carbon numbers. The magnetic properties were examined with temperature- and field-dependent magnetization measurements. As a result, we have revealed that the coercive field depends on the basal spacing. It is suggested that increasing the basal spacing varies the competition between the in-plane superexchange interactions and long-range out-of-plane dipolar interactions. Moreover, a jump in the coercive field at around 20 Å of the basal spacing is assumed to be the modification of the magnetic ordering in Co-Ni-CnSO3 LDH. PMID:27381282

  2. Effect of multivalent salts -- calcium and aluminum -- on the flocculation of kaolin suspension with anionic polyacrylamide

    SciTech Connect

    Peng, F.F.; Di, P. . Dept. of Mineral Processing Engineering)

    1994-04-01

    The effects of calcium and aluminum ions on the interaction behavior of anionic polyacrylamide (anionic PAM or HPAM) and kaolin are important in determining the efficient flocculation of kaolin. While kaolin surfaces are negatively charged in media such as water, they exhibit the positive surface charge characteristic at pH below 3.2 in the solution of calcium cation, and at pH below 9.2 in the solution of aluminum cation. The. experimental results show that both calcium and aluminum ions suppress the kaolin flocculation process. The results are analyzed and explained by molecular orbital theory, solution chemistry, infrared spectra, and electronic probe examination of kaolin treated with and without anionic PAM. Analysis results indicate that the specific adsorption of Ca[sup 2+], Al[sup 3+] and their hydroxo complexes on anionic PAM causes the loss of anionic character in the low pH range and leads to a low flocculation efficiency. In the high pH range, the poor kaolin flocculation can be attributed to precipitation of calcium and aluminum hydroxides on active functional groups, which inhibits the hydrogen bonding between anionic PAM and kaolin surfaces. At neutral pH values, the trivalent aluminum ion has more significant adverse effect on the kaolin flocculation than the divalent calcium ion.

  3. Determination of Interfacial Properties by Surface Active Impurities in an Organic Waste Liquid

    NASA Astrophysics Data System (ADS)

    Hsu, H.; Demond, A. H.

    2001-12-01

    Wettability and interfacial tension play an important role in governing the transport and distribution of the organic contaminants in the vadose zone. Organic liquids, like waste tetrachloroethylene (PCE) or gasoline, contain surface active impurities that alter the interfacial properties and, in some cases, invert the wettability depending on the pH which is controlled by the geochemistry of the system. Most studies looking at interfacial property changes utilize a single surface active impurity, while this study seeks to understand the behavior of a binary surfactant system. Individually, octanoic acid (OA) does not alter the wettability of quartz since it exists only in a netural or anionic form and cannot sorb to the negatively charged quartz surface. Dodecylamine (DDA), in its cationic form, sorbs to quartz and changes the contact angle from 5¡V70 degree, but the surface remains weakly water wetting. However, a mixture of the two changes quartz to oil wet, giving a contact angle of up to 130 degree. Similarly, the interfacial tension decreases in the mixtures more than expected based on the individual behavior of the compounds. An anionic-cationic surfactant complex is proposed to account for the change. Evidence to support this species is based on comparing the equilibrium pH values of several OA/DDA aqueous solutions with the expected pH values assuming no mutual interaction. The discrepancy between these two sets of pH values suggests that a positive-charged surfactant complex forms that may sorb on quartz. Taken together, these data show the role of pH in the formation of a hydrophobic cationic-anionic surface-active complex, and point to the importance of the synergy between geochemistry and the surface-active solutes.

  4. Imidazolium-Based Polymeric Materials as Alkaline Anion-Exchange Fuel Cell Membranes

    NASA Technical Reports Server (NTRS)

    Narayan, Sri R.; Yen, Shiao-Ping S.; Reddy, Prakash V.; Nair, Nanditha

    2012-01-01

    Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.

  5. Pulsed laser deposition of Mg-Al layered double hydroxide with Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Matei, A.; Birjega, R.; Vlad, A.; Luculescu, C.; Epurescu, G.; Stokker-Cheregi, F.; Dinescu, M.; Zavoianu, R.; Pavel, O. D.

    2013-03-01

    Powdered layered double hydroxides (LDHs)—also known as hydrotalcite-like (HT)—compounds have been widely studied due to their applications as catalysts, anionic exchangers or host materials for inorganic or organic molecules. Assembling thin films of nano-sized LDHs onto flat solid substrates is an expanding area of research, with promising applications as sensors, corrosion-resistant coatings, components in optical and magnetic devices. The exploitation of LDHs as vehicles to carry dispersed metal nanoparticles onto a substrate is a new approach to obtain composite thin films with prospects for biomedical and optical applications. We report the deposition of thin films of Ag nanoparticles embedded in a Mg-Al layered double hydroxide matrix by pulsed laser deposition (PLD). The Ag-LDH powder was prepared by co-precipitation at supersaturation and pH = 10 using aqueous solutions of Mg and Al nitrates, Na hydroxide and carbonate, and AgNO3, having atomic ratios of Mg/Al = 3 and Ag/Al = 0.55. The target to be used in laser ablation experiments was a dry pressed pellet obtained from the prepared Ag-LDH powder. Three different wavelengths of a Nd:YAG laser (266, 532 and 1064 nm) working at a repetition rate of 10 Hz were used. X-Ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and secondary ions mass spectrometry (SIMS) were used to investigate the structure, surface morphology and composition of the deposited films.

  6. Double layer hydroxide minerals as host structures for bioorganic molecules. [Abstract only

    NASA Technical Reports Server (NTRS)

    Lee, Ton; Arrhenius, Meichia L.; Hui, Stella S.-Y.; Ring, Ken M.; Gedulin, Benjamin I.; Orgel, Leslie E.; Arrhenius, Gustaf

    1994-01-01

    A central problem in molecular evolution concerns the selective concentration from dilute, multicomponent solution of source molecules into a reactive environment, where formation of larger molecular assemblages can take place. Minerals consisting of positively charged, separable metal hydroxide sheets have proven capable of these functions. This common structural type is represented by minerals such as pyroaurite (Mg-Fe(3+) hydroxide), hydrotalcite (Mg-Al), green rust Fe(2+)-Fe(3+) and others. Effective interlayer sorption is demonstrated for orthophosphate and condensed phosphates, anionic alkyl compounds, polypeptides, nucleic acids, cyanide complexes and glycolaldehyde phosphate, the latter shown to readily oligomerize to form and selectively retain racemic hexose -2, 4, 6-phosphates, preferentially of altrose (Pitsch, et al, 1993). The selective aldomerization and retention effects correlate with the charge distribution in the host mineral structure and the stereochemistry of the substrate molecules. Interaction between nucleic acid bases, and between the cyanide groups of glycolaldehyde phosphate nitrile at the low water activity in the mineral interlayer is indicated by doubling of the monomeric separation of the hydroxide mineral sheets.

  7. Anticancer nanodelivery system with controlled release property based on protocatechuate–zinc layered hydroxide nanohybrid

    PubMed Central

    Barahuie, Farahnaz; Hussein, Mohd Zobir; Abd Gani, Shafinaz; Fakurazi, Sharida; Zainal, Zulkarnain

    2014-01-01

    Background We characterize a novel nanocomposite that acts as an efficient anticancer agent. Methods This nanocomposite consists of zinc layered hydroxide intercalated with protocatechuate (an anionic form of protocatechuic acid), that has been synthesized using a direct method with zinc oxide and protocatechuic acid as precursors. Results The resulting protocatechuic acid nanocomposite (PAN) showed a basal spacing of 12.7 Å, indicating that protocatechuate was intercalated in a monolayer arrangement, with an angle of 54° from the Z-axis between the interlayers of the zinc layered hydroxide, and an estimated drug loading of about 35.7%. PAN exhibited the properties of a mesoporous type material, with greatly enhanced thermal stability of protocatechuate as compared to its free counterpart. The presence of protocatechuate in the interlayers of the zinc layered hydroxide was further supported by Fourier transform infrared spectroscopy. Protocatechuate was released from PAN in a slow and sustained manner. This mechanism of release was well represented by a pseudo-second order kinetics model. PAN has shown increased cytotoxicity compared to the free form of protocatechuic acid in all cancer cell lines tested. Tumor growth suppression was extensive, particularly in HepG2 and HT29 cell lines. Conclusion PAN is suitable for use as a controlled release formulation, and our in vitro evidence indicates that PAN is an effective anticancer agent. PAN may have potential as a chemotherapeutic drug for human cancer. PMID:25061291

  8. Anion Transport with Chalcogen Bonds.

    PubMed

    Benz, Sebastian; Macchione, Mariano; Verolet, Quentin; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2016-07-27

    In this report, we introduce synthetic anion transporters that operate with chalcogen bonds. Electron-deficient dithieno[3,2-b;2',3'-d]thiophenes (DTTs) are identified as ideal to bind anions in the focal point of the σ holes on the cofacial endocyclic sulfur atoms. Anion binding in solution and anion transport across lipid bilayers are found to increase with the depth of the σ holes of the DTT anionophores. These results introduce DTTs and related architectures as a privileged motif to engineer chalcogen bonds into functional systems, complementary in scope to classics such as 2,2'-bipyrroles or 2,2'-bipyridines that operate with hydrogen bonds and lone pairs, respectively. PMID:27433964

  9. The interfacial interactions of Tb-doped silica nanoparticles with surfactants and phospholipids revealed through the fluorescent response.

    PubMed

    Bochkova, Olga D; Mustafina, Asiya R; Mukhametshina, Alsu R; Burilov, Vladimir A; Skripacheva, Viktoriya V; Zakharova, Lucia Ya; Fedorenko, Svetlana V; Konovalov, Alexander I; Soloveva, Svetlana E; Antipin, Igor S

    2012-04-01

    The quenching effect of dyes (phenol red and bromothymol blue) on Tb(III)-centered luminescence enables to sense the aggregation of cationic and anionic surfactants near the silica surface of Tb-doped silica nanoparticles (SN) in aqueous solutions. The Tb-centered luminescence of non-decorated SNs is diminished by the inner filter effect of both dyes. The decoration of the silica surface by cationic surfactants induces the quenching through the energy transfer between silica coated Tb(III) complexes and dye anions inserted into surfactant aggregates. Thus the distribution of surfactants aggregates at the silica/water interface and in the bulk of solution greatly affects dynamic quenching efficiency. The displacement of dye anions from the interfacial surfactant adlayer by anionic surfactants and phospholipids is accompanied by the "off-on" switching of Tb(III)-centered luminescence. PMID:22209651

  10. Structural transformation of nickel hydroxide films during anodic oxidation

    SciTech Connect

    Crocker, R.W.; Muller, R.H.

    1992-05-01

    The transformation of anodically formed nickel hydroxide/oxy-hydroxide electrodes has been investigated. A mechanism is proposed for the anodic oxidation reaction, in which the reaction interface between the reduced and oxidized phases of the electrode evolves in a nodular topography that leads to inefficient utilization of the active electrode material. In the proposed nodular transformation model for the anodic oxidation reaction, nickel hydroxide is oxidized to nickel oxy-hydroxide in the region near the metal substrate. Since the nickel oxy-hydroxide is considerably more conductive than the surrounding nickel hydroxide, as further oxidation occurs, nodular features grow rapidly to the film/electrolyte interface. Upon emerging at the electrolyte interface, the reaction boundary between the nickel hydroxide and oxy-hydroxide phases spreads laterally across the film/electrolyte interface, creating an overlayer of nickel oxy-hydroxide and trapping uncharged regions of nickel hydroxide within the film. The nickel oxy-hydroxide overlayer surface facilitates the oxygen evolution side reaction. Scanning tunneling microscopy of the electrode in its charged state revealed evidence of 80 {endash} 100 Angstrom nickel oxy-hydroxide nodules in the nickel hydroxide film. In situ spectroscopic ellipsometer measurements of films held at various constant potentials agree quantitatively with optical models appropriate to the nodular growth and subsequent overgrowth of the nickel oxy-hydroxide phase. A two-dimensional, numerical finite difference model was developed to simulate the current distribution along the phase boundary between the charged and uncharged material. The model was used to explore the effects of the physical parameters that govern the electrode behavior. The ratio of the conductivities of the nickel hydroxide and oxy-hydroxide phases was found to be the dominant parameter in the system.

  11. Towards high conductivity in anion-exchange membranes for alkaline fuel cells.

    PubMed

    Li, Nanwen; Guiver, Michael D; Binder, Wolfgang H

    2013-08-01

    Quaternized poly(2,6-dimethylphenylene oxide) materials (PPOs) containing clicked 1,2,3-triazoles were first prepared through Cu(I) -catalyzed "click chemistry" to improve the anion transport in anion-exchange membranes (AEMs). Clicked 1,2,3-triazoles incorporated into AEMs provided more sites to form efficient and continuous hydrogen-bond networks between the water/hydroxide and the triazole for anion transport. Higher water uptake was observed for these triazole membranes. Thus, the membranes showed an impressive enhancement of the hydroxide diffusion coefficient and, therefore, the anion conductivities. The recorded hydroxide conductivity was 27.8-62 mS cm(-1) at 20 °C in water, which was several times higher than that of a typical PPO-based AEM (TMA-20) derived from trimethylamine (5 mS cm(-1) ). Even at reduced relative humidity, the clicked membrane showed superior conductivity to a trimethylamine-based membrane. Moreover, similar alkaline stabilities at 80 °C in 1 M NaOH were observed for the clicked and non-clicked membranes. The performance of a H2 /O2 single cell assembled with a clicked AEM was much improved compared to that of a non-clicked TMA-20 membrane. The peak power density achieved for an alkaline fuel cell with the synthesized membrane 1a(20) was 188.7 mW cm(-2) at 50 °C. These results indicated that clicked AEM could be a viable strategy for improving the performance of alkaline fuel cells.

  12. Recycling Lithium Carbonate/Lithium Hydroxide Waste

    NASA Technical Reports Server (NTRS)

    Flowers, J.; Flowers, J.

    1983-01-01

    Hazardous waste disposal problem eliminated by regeneration. Li2CO3/ LiOH recycling process relies on low solubility of alkali carbonates in corresponding hydroxides. Li2CO3 precipitate calcined to LI2O, then rehydrated LiOH. Regeneration eliminates need to dispose caustic waste and uses less energy than simple calcination of entire waste mass.

  13. 21 CFR 184.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... ingredient as generally recognized as safe (GRAS) as a direct human food ingredient is based upon the... water additive complying with § 173.310 of this chapter. (2) The ingredient is used in food at levels... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ammonium hydroxide. 184.1139 Section 184.1139...

  14. 21 CFR 184.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... ingredient as generally recognized as safe (GRAS) as a direct human food ingredient is based upon the... water additive complying with § 173.310 of this chapter. (2) The ingredient is used in food at levels... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ammonium hydroxide. 184.1139 Section 184.1139...

  15. 21 CFR 184.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... ingredient as generally recognized as safe (GRAS) as a direct human food ingredient is based upon the... water additive complying with § 173.310 of this chapter. (2) The ingredient is used in food at levels... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ammonium hydroxide. 184.1139 Section 184.1139...

  16. 21 CFR 184.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... ingredient as generally recognized as safe (GRAS) as a direct human food ingredient is based upon the... water additive complying with § 173.310 of this chapter. (2) The ingredient is used in food at levels... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ammonium hydroxide. 184.1139 Section 184.1139...

  17. Synthesis, characterization and application of two-dimensional layered metal hydroxides for environmental remediation purposes

    NASA Astrophysics Data System (ADS)

    Machingauta, Cleopas

    Two-dimensional layered nano composites, which include layered double hydroxides (LDHs), hydroxy double salts (HDSs) and layered hydroxide salts (LHSs) are able to intercalate different molecular species within their gallery space. These materials have a tunable structural composition which has made them applicable as fire retardants, adsorbents, catalysts, catalyst support materials, and ion exchangers. Thermal treatment of these materials results in destruction of the layers and formation of mixed metal oxides (MMOs) and spinels. MMOs have the ability to adsorb anions from solution and may also regenerate layered structures through a phenomenon known as memory effect. Zinc-nickel hydroxy nitrate was used for the uptake of a series of halogenated acetates (HAs). HAs are pollutants introduced into water systems as by-products of water chlorination and pesticide degradation; their sequestration from water is thus crucial. Optimization of layered materials for controlled uptake requires an understanding of their ion-exchange kinetics and thermodynamics. Exchange kinetics of these anions was monitored using ex-situ PXRD, UV-vis, HPLC and FTIR. It was revealed that exchange rates and uptake efficiencies are related to electronic spatial extents and the charge on carboxyl-oxygen atoms. In addition, acetate and nitrate-based HDSs were used to explore how altering the hydroxide layer affects uptake of acetate/nitrate ions. Changing the metal identities affects the interaction of the anions with the layers. From FTIR, we observed that nitrates coordinate in a D3h and Cs/C 2v symmetry; the nitrates in D3h symmetry were easily exchangeable. Interlayer hydrogen bonding was also revealed to be dependent on metal identity. Substituting divalent cations with trivalent cations produces materials with a higher charge density than HDSs and LHSs. A comparison of the uptake efficiency of zinc-aluminum, zinc-gallium and zinc-nickel hydroxy nitrates was performed using trichloroacetic

  18. Study of nickel hydroxide electrodes. 2: Oxidation products of nickel (2) hydroxides

    NASA Technical Reports Server (NTRS)

    Bode, H.; Demelt, K.; White, J.

    1986-01-01

    Pure phases of some oxidized Ni oxides were prepared galvanimetrically with the Ni(2) hydroxide electrode of an alkaline battery. The crystallographic data of these phases, their chemical behavior, and conditions of transition were studied.

  19. [Interfacial area and interfacial transfer in two-phase flow

    SciTech Connect

    Ishii, M.

    1993-09-01

    A joint research program funded by the DOE/BES at Purdue University and the University of Wisconsin-Milwaukee has been underway. The main efforts of the Purdue program were concentrated on the following tasks. Development of Four Sensor Measurement Method; Experimental Study of Axial Changes of Transverse Void and Interfacial Area Profiles in Bubbly Flow; Modeling of the Probe-Particle Interaction Using Monte Carlo Numerical Simulation; and Experimental Study of the Stability of Interface of Very Large Bubbles. Highlights of these research results are reported.

  20. Behaviour of the surface hydroxide groups of exfoliated kaolinite in the gas phase and during water adsorption.

    PubMed

    Táborosi, Attila; Szilágyi, Róbert K

    2016-02-14

    The chemical and physical properties, and thus the reactivity of phylloaluminosilicates can be tailored by intercalation, delamination, and exfoliation processes. In going from the periodic crystalline to the molecular exfoliated phase, surface defects and modifications gain importance as each face of the phylloaluminosilicate comes in direct contact with the external chemical environment. In this work, we extend our earlier studies on the molecular cluster modelling of exfoliated kaolinite sheets by evaluating the positions and orientations of surface hydroxide groups and bridging oxide anions, as the sites of reactivity. The previous focus on the inner chemical environment of a single kaolinite layer is shifted to the surface exposed octahedral aluminium-hydroxide and tetrahedral silicon-oxide sheets. The combination of semi-empirical, ab initio wave function, and density functional calculations unanimously support the amphoteric nature of the surface hydroxide groups with respect to H-bonding donor/acceptor capabilities. To a lesser extent, we observe the same for the bridging oxide anions. This is in contrast to the crystalline phase, which manifests only donor orientation for maintaining an inter-layer H-bond network. These results suggest that both electrophilic and nucleophilic characteristics of the octahedral and tetrahedral sheets need to be considered during intercalation and concomitant exfoliation of the kaolinite sheets.

  1. Behaviour of the surface hydroxide groups of exfoliated kaolinite in the gas phase and during water adsorption.

    PubMed

    Táborosi, Attila; Szilágyi, Róbert K

    2016-02-14

    The chemical and physical properties, and thus the reactivity of phylloaluminosilicates can be tailored by intercalation, delamination, and exfoliation processes. In going from the periodic crystalline to the molecular exfoliated phase, surface defects and modifications gain importance as each face of the phylloaluminosilicate comes in direct contact with the external chemical environment. In this work, we extend our earlier studies on the molecular cluster modelling of exfoliated kaolinite sheets by evaluating the positions and orientations of surface hydroxide groups and bridging oxide anions, as the sites of reactivity. The previous focus on the inner chemical environment of a single kaolinite layer is shifted to the surface exposed octahedral aluminium-hydroxide and tetrahedral silicon-oxide sheets. The combination of semi-empirical, ab initio wave function, and density functional calculations unanimously support the amphoteric nature of the surface hydroxide groups with respect to H-bonding donor/acceptor capabilities. To a lesser extent, we observe the same for the bridging oxide anions. This is in contrast to the crystalline phase, which manifests only donor orientation for maintaining an inter-layer H-bond network. These results suggest that both electrophilic and nucleophilic characteristics of the octahedral and tetrahedral sheets need to be considered during intercalation and concomitant exfoliation of the kaolinite sheets. PMID:26705545

  2. 21 CFR 73.1010 - Alumina (dried aluminum hydroxide).

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Alumina (dried aluminum hydroxide). 73.1010... GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1010 Alumina (dried aluminum hydroxide). (a) Identity. (1) The color additive alumina (dried aluminum hydroxide) is a white,...

  3. 21 CFR 73.1010 - Alumina (dried aluminum hydroxide).

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Alumina (dried aluminum hydroxide). 73.1010... GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1010 Alumina (dried aluminum hydroxide). (a) Identity. (1) The color additive alumina (dried aluminum hydroxide) is a white,...

  4. 21 CFR 73.1010 - Alumina (dried aluminum hydroxide).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Alumina (dried aluminum hydroxide). 73.1010... GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1010 Alumina (dried aluminum hydroxide). (a) Identity. (1) The color additive alumina (dried aluminum hydroxide) is a white,...

  5. 21 CFR 73.1010 - Alumina (dried aluminum hydroxide).

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Alumina (dried aluminum hydroxide). 73.1010... GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1010 Alumina (dried aluminum hydroxide). (a) Identity. (1) The color additive alumina (dried aluminum hydroxide) is a white,...

  6. 21 CFR 73.1010 - Alumina (dried aluminum hydroxide).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Alumina (dried aluminum hydroxide). 73.1010... GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1010 Alumina (dried aluminum hydroxide). (a) Identity. (1) The color additive alumina (dried aluminum hydroxide) is a white,...

  7. 40 CFR 721.10504 - Surface modified magnesium hydroxide (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Surface modified magnesium hydroxide... Specific Chemical Substances § 721.10504 Surface modified magnesium hydroxide (generic). (a) Chemical... as surface modified magnesium hydroxide (PMN P-06-682) is subject to reporting under this section...

  8. 40 CFR 721.10504 - Surface modified magnesium hydroxide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Surface modified magnesium hydroxide... Specific Chemical Substances § 721.10504 Surface modified magnesium hydroxide (generic). (a) Chemical... as surface modified magnesium hydroxide (PMN P-06-682) is subject to reporting under this section...

  9. 21 CFR 872.3250 - Calcium hydroxide cavity liner.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Calcium hydroxide cavity liner. 872.3250 Section... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3250 Calcium hydroxide cavity liner. (a) Identification. A calcium hydroxide cavity liner is a device material intended to be applied to the interior of...

  10. 21 CFR 872.3250 - Calcium hydroxide cavity liner.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Calcium hydroxide cavity liner. 872.3250 Section... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3250 Calcium hydroxide cavity liner. (a) Identification. A calcium hydroxide cavity liner is a device material intended to be applied to the interior of...

  11. 21 CFR 872.3250 - Calcium hydroxide cavity liner.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Calcium hydroxide cavity liner. 872.3250 Section... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3250 Calcium hydroxide cavity liner. (a) Identification. A calcium hydroxide cavity liner is a device material intended to be applied to the interior of...

  12. 40 CFR 721.4600 - Recovered metal hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Recovered metal hydroxide. 721.4600... Substances § 721.4600 Recovered metal hydroxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a recovered metal hydroxide (PMN...

  13. 40 CFR 721.4600 - Recovered metal hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Recovered metal hydroxide. 721.4600... Substances § 721.4600 Recovered metal hydroxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a recovered metal hydroxide (PMN...

  14. 40 CFR 721.4600 - Recovered metal hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Recovered metal hydroxide. 721.4600... Substances § 721.4600 Recovered metal hydroxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a recovered metal hydroxide (PMN...

  15. 40 CFR 721.4600 - Recovered metal hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Recovered metal hydroxide. 721.4600... Substances § 721.4600 Recovered metal hydroxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a recovered metal hydroxide (PMN...

  16. 40 CFR 721.4600 - Recovered metal hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Recovered metal hydroxide. 721.4600... Substances § 721.4600 Recovered metal hydroxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a recovered metal hydroxide (PMN...

  17. 21 CFR 73.2326 - Chromium hydroxide green.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium hydroxide green. 73.2326 Section 73.2326... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2326 Chromium hydroxide green. (a) Identity and specifications.The color additive chromium hydroxide green shall conform in identity and specifications to...

  18. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Chromium hydroxide green. 73.1326 Section 73.1326... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1326 Chromium hydroxide green. (a) Identity. (1) The color additive chromium hydroxide green is principally hydrated chromic sesquioxide...

  19. 21 CFR 73.2326 - Chromium hydroxide green.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Chromium hydroxide green. 73.2326 Section 73.2326... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2326 Chromium hydroxide green. (a) Identity and specifications.The color additive chromium hydroxide green shall conform in identity and specifications to...

  20. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium hydroxide green. 73.1326 Section 73.1326... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1326 Chromium hydroxide green. (a) Identity. (1) The color additive chromium hydroxide green is principally hydrated chromic sesquioxide...

  1. Anion exchange polymer electrolytes

    DOEpatents

    Kim, Yu Seung; Kim, Dae Sik; Lee, Kwan-Soo

    2013-07-23

    Solid anion exchange polymer electrolytes and compositions comprising chemical compounds comprising a polymeric core, a spacer A, and a guanidine base, wherein said chemical compound is uniformly dispersed in a suitable solvent and has the structure: ##STR00001## wherein: i) A is a spacer having the structure O, S, SO.sub.2, --NH--, --N(CH.sub.2).sub.n, wherein n=1-10, --(CH.sub.2).sub.n--CH.sub.3--, wherein n=1-10, SO.sub.2-Ph, CO-Ph, ##STR00002## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 each are independently --H, --NH.sub.2, F, Cl, Br, CN, or a C.sub.1-C.sub.6 alkyl group, or any combination of thereof; ii) R.sub.9, R.sub.10, R.sub.11, R.sub.12, or R.sub.13 each independently are --H, --CH.sub.3, --NH.sub.2, --NO, --CH.sub.nCH.sub.3 where n=1-6, HC.dbd.O--, NH.sub.2C.dbd.O--, --CH.sub.nCOOH where n=1-6, --(CH.sub.2).sub.n--C(NH.sub.2)--COOH where n=1-6, --CH--(COOH)--CH.sub.2--COOH, --CH.sub.2--CH(O--CH.sub.2CH.sub.3).sub.2, --(C.dbd.S)--NH.sub.2, --(C.dbd.NH)--N--(CH.sub.2).sub.nCH.sub.3, where n=0-6, --NH--(C.dbd.S)--SH, --CH.sub.2--(C.dbd.O)--O--C(CH.sub.3).sub.3, --O--(CH.sub.2).sub.n--CH--(NH.sub.2)--COOH, where n=1-6, --(CH.sub.2).sub.n--CH.dbd.CH wherein n=1-6, --(CH.sub.2).sub.n--CH--CN wherein n=1-6, an aromatic group such as a phenyl, benzyl, phenoxy, methylbenzyl, nitrogen-substituted benzyl or phenyl groups, a halide, or halide-substituted methyl groups; and iii) wherein the composition is suitable for use in a membrane electrode assembly.

  2. Bound anionic states of adenine

    SciTech Connect

    Haranczyk, Maciej; Gutowski, Maciej S; Li, Xiang; Bowen, Kit H

    2007-03-20

    Anionic states of nucleic acid bases are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated nucleic acid base parent anions probed only dipole-bound states, which are not present in condensed phase environments, but did not observe valence anionic states, which for purine bases, are thought to be adiabatically unbound. Contrary to this expectation, we have demonstrated that some thus far ignored tautomers of adenine, which result from enamine-imine transformations, support valence anionic states with electron vertical detachment energies as large as 2.2 eV, and at least one of these anionic tautomers is adiabatically bound. Moreover, we predict that the new anionic tautomers should also dominate in solutions and should be characterized by larger values of electron vertical detachment energy than the canonical valence anion. All of the new-found anionic tautomers might be formed in the course of dissociative electron attachment followed by a hydrogen atom attachment to a carbon atom, and they might affect the structure and properties of DNA and RNA exposed to low-energy electrons. The discovery of these valence anionic states of adenine was facilitated by the development of: (i) a new experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (ii) a new combinatorial/ quantum chemical approach for identification of the most stable tautomers of organic molecules. The computational portion of this work was supported by the: (i) Polish State Committee for Scientific Research (KBN) Grants: DS/8000-4-0140-7 (M.G.) and N204 127 31/2963 (M.H.), (ii) European Social Funds (EFS) ZPORR/2.22/II/2.6/ARP/U/2/05 (M.H.), and (iii) US DOE Office of Biological and Environmental Research, Low Dose Radiation Research Program (M.G.). M.H. holds the Foundation for Polish Science (FNP) award for young scientists. The calculations were performed at the Academic

  3. Measuring Interfacial Tension Between Immiscible Liquids

    NASA Technical Reports Server (NTRS)

    Rashidnia, Nasser; Balasubramaniam, R.; Delsignore, David M.

    1995-01-01

    Glass capillary tube technique measures interfacial tension between two immiscible liquids. Yields useful data over fairly wide range of interfacial tensions, both for pairs of liquids having equal densities and pairs of liquids having unequal densities. Data on interfacial tensions important in diverse industrial chemical applications, including enhanced extraction of oil; printing; processing foods; and manufacture of paper, emulsions, foams, aerosols, detergents, gel encapsulants, coating materials, fertilizers, pesticides, and cosmetics.

  4. Interfacial reactions between titanium and borate glass

    SciTech Connect

    Brow, R.K.; Saha, S.K.; Goldstein, J.I.

    1992-12-31

    Interfacial reactions between melts of several borate glasses and titanium have been investigated by analytical scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS). A thin titanium boride interfacial layer is detected by XPS after short (30 minutes) thermal treatments. ASEM analyses after longer thermal treatments (8--120 hours) reveal boron-rich interfacial layers and boride precipitates in the Ti side of the interface.

  5. Electrocoagulation mechanism of perfluorooctanoate (PFOA) on a zinc anode: Influence of cathodes and anions.

    PubMed

    Wang, Yujuan; Lin, Hui; Jin, Fangyuan; Niu, Junfeng; Zhao, Jinbo; Bi, Ying; Li, Ying

    2016-07-01

    Batch experiments were conducted to investigate the effects of cathode materials and anions (Cl(-), SO4(2-), NO3(-), and CO3(2-)/HCO3(-)) on perfluorooctanoate (PFOA) removal in electrocoagulation process using zinc anode. The results indicated that the hydroxide flocs generated in-situ in the electrocoagulation process using the stainless steel rod as cathode were more effective than those using aluminum rod as cathode for the removal of PFOA after 20min of electrocoagulation at a current density of 0.5mAcm(-2). Hydroxide flocs generated in-situ in the electrocoagulation in the presence of Cl(-)/NO3(-) could effectively remove PFOA from aqueous solution with the removal ratios of 99.7%/98.1% and 98.9%/97.3% using stainless steel rod and aluminum rod as cathode, respectively. However, the PFOA removal ratios were 96.2%/4.1% and 7.4%/4.6% using stainless steel rod and aluminum rod as cathode, respectively, in the presence of SO4(2-) and CO3(2-)/HCO3(-). The different removal ratios of PFOA during the electrocoagulation process were primarily due to the fact that the hydroxide flocs generated in-situ were different in the presence of diverse cathodes and anions. We firstly demonstrated that Zn0.70Al0.30(OH)2(CO3)0.15·xH2O and ZnO generated in-situ in the electrocoagulation process (except for CO3(2-)/HCO3(-)) using zinc anode and aluminum/stainless steel rod cathode governed the sorption of PFOA. The adsorbent hydroxide flocs in-situ generated in the presence of Cl(-) could effectively remove PFOA from aqueous solution containing CO3(2-)/HCO3(-) anion at the initial hydroxide flocs concentration of 2000mgL(-1). These results provided an effective and alternative method to remove PFOA from aqueous solution containing CO3(2-)/HCO3(-) anion.

  6. Aprotic Heterocyclic Anion Triazolide Ionic Liquids - A New Class of Ionic Liquid Anion Accessed by the Huisgen Cycloaddition Reaction

    SciTech Connect

    Thompson, Robert L; Damodaran, Krishnan; Luebke, David; Nulwala, Hunaid

    2013-06-01

    The triazole core is a highly versatile heterocyclic ring which can be accessed easily with the Cu(I)-catalyzed Huisgen cycloaddition reaction. Herein we present the preparation of ionic liquids that incorporate a 1,2,3-triazolide anion. These ionic liquids were prepared by a facile procedure utilizing a base-labile pivaloylmethyl group at the 1-position, which can act as precursors to 1H- 4-substituted 1,2,3-triazole. These triazoles were then subsequently converted into ionic liquids after deprotonation using an appropriate ionic liquid cation hydroxide. The densities and thermal decompositions of these ionic liquids were measured. These novel ionic liquids have potential applications in gas separations and in metal-free catalysis.

  7. Oxygen isotope indicators of selenate reaction with Fe(II) and Fe(III) hydroxides.

    PubMed

    Schellenger, Alexandra E P; Larese-Casanova, Philip

    2013-06-18

    Selenate (SeO(4)(2-)) reduction to elemental selenium is an important Se immobilization process in subsurface environments that could be mediated by Fe(II)-rich minerals or selenate-respiring microorganisms. We report the kinetic isotope effects for (18)O within selenate during abiotic reactions with iron-bearing hydroxides within laboratory experiments. Selenate was reduced to Se(0) by a green rust (chloride interlayer type) and ferrous hydroxide, the two known environmentally relevant mineral reductants for selenate. Reaction kinetics are described by a rapid, low-fractionating uptake step caused by diffusive exchange between selenate and chloride followed by a slower, high-fractionating reduction step caused by electron transfer from structural Fe(II). The dual-phase kinetics cannot be described with the traditional Rayleigh fractionation model; however, well after the initial uptake step, the extent of selenate reaction is well correlated with δ(18)O values in accordance with the Rayleigh model. Selenate-(18)O enrichment (εO) was nearly identical for reaction with chloride green rust (22.7 ± 2.2‰) and ferrous hydroxide (22.1 ± 1.1‰) which suggests a common reduction mechanism by structural Fe(II). The minor enrichment due to anion exchange alone (1.4 ± 0.2‰) was confirmed using iowaite, a nonredox active Mg(II)-Fe(III) layered double hydroxide. Our εO results may contribute to Se isotope forensics to identify selenate reduction within field sites and to possibly distinguish between abiotic and biotic reduction processes.

  8. Interfacial ionic ‘liquids’: connecting static and dynamic structures

    DOE PAGES

    Uysal, Ahmet; Zhou, Hua; Feng, Guang; Lee, Sang Soo; Li, Song; Cummings, Peter T.; Fulvio, Pasquale F.; Dai, Sheng; McDonough, John K.; Gogotsi, Yury; et al

    2014-12-05

    It is well known that room temperature ionic liquids (RTILs) often adopt a charge-separated layered structure, i.e. with alternating cation- and anion-rich layers, at electrified interfaces. However, the dynamic response of the layered structure to temporal variations in applied potential is not well understood. In this study, we used in situ, real-time x-ray reflectivity to study the potential-dependent electric double layer (EDL) structure of an imidazolium-based RTIL on charged epitaxial graphene during potential cycling as a function of temperature. The results suggest that the graphene–RTIL interfacial structure is bistable in which the EDL structure at any intermediate potential can bemore » described by the combination of two extreme-potential structures whose proportions vary depending on the polarity and magnitude of the applied potential. This picture is supported by the EDL structures obtained by fully atomistic molecular dynamics simulations at various static potentials. The potential-driven transition between the two structures is characterized by an increasing width but with an approximately fixed hysteresis magnitude as a function of temperature. Finally, the results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (~0.15 eV).« less

  9. Interfacial ionic ‘liquids’: connecting static and dynamic structures

    SciTech Connect

    Uysal, Ahmet; Zhou, Hua; Feng, Guang; Lee, Sang Soo; Li, Song; Cummings, Peter T.; Fulvio, Pasquale F.; Dai, Sheng; McDonough, John K.; Gogotsi, Yury; Fenter, Paul

    2014-12-05

    It is well known that room temperature ionic liquids (RTILs) often adopt a charge-separated layered structure, i.e. with alternating cation- and anion-rich layers, at electrified interfaces. However, the dynamic response of the layered structure to temporal variations in applied potential is not well understood. In this study, we used in situ, real-time x-ray reflectivity to study the potential-dependent electric double layer (EDL) structure of an imidazolium-based RTIL on charged epitaxial graphene during potential cycling as a function of temperature. The results suggest that the graphene–RTIL interfacial structure is bistable in which the EDL structure at any intermediate potential can be described by the combination of two extreme-potential structures whose proportions vary depending on the polarity and magnitude of the applied potential. This picture is supported by the EDL structures obtained by fully atomistic molecular dynamics simulations at various static potentials. The potential-driven transition between the two structures is characterized by an increasing width but with an approximately fixed hysteresis magnitude as a function of temperature. Finally, the results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (~0.15 eV).

  10. Understanding Arsenate Reaction Kinetics with Ferric Hydroxides

    PubMed Central

    Farrell, James; Chaudhary, Binod K.

    2015-01-01

    Understanding arsenic reactions with ferric hydroxides is important in understanding arsenic transport in the environment and in designing systems for removing arsenic from potable water. Many experimental studies have shown that the kinetics of arsenic adsorption on ferric hydroxides is biphasic, where a fraction of the arsenic adsorption occurs on a time scale of seconds while full equilibrium may require weeks to attain. This research employed density functional theory modeling in order to understand the mechanisms contributing to biphasic arsenic adsorption kinetics. The reaction energies and activation barriers for three modes of arsenate adsorption to ferric hydroxides were calculated. Gibbs free energies of reaction depended on the net charge of the complexes, which is a function of the system pH value. Physical adsorption of arsenate to ferric hydroxide proceeded with no activation barrier, with Gibbs free energies of reaction ranging from −21 to −58 kJ/mol. The highest Gibbs free energies of reaction for physical adsorption resulted from negative charge assisted hydrogen bonding between H atoms on the ferric hydroxide and O atoms in arsenate. The conversion of physically adsorbed arsenate into monodentate surface complexes had Gibbs free energies of activation ranging from 62 to 73 kJ/mol, and Gibbs free energies of reaction ranging from −23 to −38 kJ/mol. The conversion of monodentate surface complexes to bidentate, binuclear complexes had Gibbs free energies of activation ranging from 79 to 112 kJ/mol, and Gibbs free energies of reaction ranging from −11 to −55 kJ/mol. For release of arsenate from uncharged bidentate complexes, energies of activation as high as 167 kJ/mol were encountered. Increasingly negative charges on the complexes lowered the activation barriers for desorption of arsenate, and in complexes with −2 charges, the highest activation barrier was 65 kJ/mol. This study shows that the slow kinetics associated with arsenic

  11. Protein interfacial structure and nanotoxicology

    NASA Astrophysics Data System (ADS)

    White, John W.; Perriman, Adam W.; McGillivray, Duncan J.; Lin, Jhih-Min

    2009-02-01

    Here we briefly recapitulate the use of X-ray and neutron reflectometry at the air-water interface to find protein structures and thermodynamics at interfaces and test a possibility for understanding those interactions between nanoparticles and proteins which lead to nanoparticle toxicology through entry into living cells. Stable monomolecular protein films have been made at the air-water interface and, with a specially designed vessel, the substrate changed from that which the air-water interfacial film was deposited. This procedure allows interactions, both chemical and physical, between introduced species and the monomolecular film to be studied by reflectometry. The method is briefly illustrated here with some new results on protein-protein interaction between β-casein and κ-casein at the air-water interface using X-rays. These two proteins are an essential component of the structure of milk. In the experiments reported, specific and directional interactions appear to cause different interfacial structures if first, a β-casein monolayer is attacked by a κ-casein solution compared to the reverse. The additional contrast associated with neutrons will be an advantage here. We then show the first results of experiments on the interaction of a β-casein monolayer with a nanoparticle titanium oxide sol, foreshadowing the study of the nanoparticle "corona" thought to be important for nanoparticle-cell wall penetration.

  12. Convection and interfacial mass exchange

    NASA Astrophysics Data System (ADS)

    Colinet, P.; Legros, J. C.; Dauby, P. C.; Lebon, G.; Bestehorn, M.; Stephan, P.; Tadrist, L.; Cerisier, P.; Poncelet, D.; Barremaecker, L.

    2005-10-01

    Mass-exchange through fluid interfaces is ubiquitous in many natural and industrial processes. Yet even basic phase-change processes such as evaporation of a pure liquid are not fully understood, in particular when coupled with fluid motions in the vicinity of the phase-change interface, or with microscopic physical phenomena in the vicinity of a triple line (where the interface meets a solid). Nowadays, many industries recognise that this lack of fundamental knowledge is hindering the optimisation of existing processes. Their modelling tools are too dependent on empirical correlations with a limited - and often unknown - range of applicability. In addition to the intrinsic multiscale nature of the phenomena involved in typical industrial processes linked to interfacial mass exchange, their study is highly multi-disciplinary, involving tools and techniques belonging to physical chemistry, chemical engineering, fluid dynamics, non-linear physics, non-equilibrium thermodynamics, chemistry and statistical physics. From the experimental point of view, microgravity offers a unique environment to obtain valuable data on phase-change processes, greatly reducing the influence of body forces and allowing the detailed and accurate study of interfacial dynamics. In turn, such improved understanding leads to optimisation of industrial processes and devices involving phase-change, both for space and ground applications.

  13. Sinusoidal Forcing of Interfacial Films

    NASA Astrophysics Data System (ADS)

    Rasheed, Fayaz; Raghunandan, Aditya; Hirsa, Amir; Lopez, Juan

    2015-11-01

    Fluid transport, in vivo, is accomplished via pumping mechanisms of the heart and lungs, which results in biological fluids being subjected to oscillatory shear. Flow is known to influence biological macromolecules, but predicting the effect of shear is incomplete without also accounting for the influence of complex interfaces ubiquitous throughout the body. Here, we investigated the oscillatory response of the structure of aqueous interfacial films using a cylindrical knife edge viscometer. Vitamin K1 was used as a model monolayer because its behaviour has been thoroughly quantified and it doesn't show any measurable hysteresis. The monolayer was subjected to sinusoidal forcing under varied conditions of surface concentrations, periodic frequencies, and knife edge amplitudes. Particle Image Velocimetry(PIV) data was collected using Brewster Angle Microscopy(BAM), revealing the influence of oscillatory interfacial shear stress on the monolayer. Insights were gained as to how the velocity profile dampens at specific distances from the knife edge contact depending on the amplitude, frequency, and concentration of Vitamin K1. Supported by NNX13AQ22G, National Aeronautics and Space Administration.

  14. Metal (Hydr)oxides for the removal of Cr(VI) from drinking water: a XAFS study

    NASA Astrophysics Data System (ADS)

    Pinakidou, F.; Kaprara, E.; Katsikini, M.; Paloura, E. C.; Simeonidis, K.; Mitrakas, M.

    2016-05-01

    The reduction mechanism and adsorption behaviour of Cr(VI) onto Tin(II) oxy- hydroxides are investigated using Cr-K edge X-ray absorption fine structure (XAFS) spectroscopies. The synthesis of the Sn oxy-hydroxide proceeds via hydrolysis of SnSO4. The successful reduction of Cr(VI) was identified by the analysis of the Cr-K edge XANES spectra where only Cr(III) species in octahedral sites are detected. According to the Cr-K edge EXAFS analysis results, Cr(III) forms bidentate inner sphere (binuclear (2C) and mononuclear (2E)) complexes. However, the surface coverage of Cr affects the type of Cr(III)-complexes formed: as the Cr-loading increases, Cr(III)-oxy-anions preferentially sorb in a “combined” 2C and 1V configuration, at the expense of the existing 2E sorption geometry.

  15. Distribution of anionic groups at the cell surface of different Sporothrix schenckii cell types.

    PubMed

    Benchimol, M; de Souza, W; Travassos, L R

    1979-06-01

    The distribution of anionic groups at the cell surface of yeastlike forms, hyphae, and conidia of Sporothrix schenckii was studied by staining with colloidal iron hydroxide and cationized ferritin. By using colloidal iron hydroxide it was shown that the external cell wall layer of one strain (strain 1099.18) could be resolved into two reactive sublayers and that these layers were present in many but not all cells of the same population. In contrast, most cells of another strain (strain 1099.12) were stained by colloidal iron hydroxide, but only one reactive layer was seen. Acidic layers of the yeastlike forms of the two strains were much thicker than those of conidia and hyphae. By the cationized ferritin staining procedure it was observed that the acidic layers of yeast forms sloughed off of cells, probably due to cell-cell or cell-medium attrition in shaken submerged cultures or to a process by which the outer layers detach from cells as they are replaced by newly synthesized ones. The colloidal iron hydroxide- and cationized ferritin-reactive cell surface layers of S. schenckii correspond to the previously described (L. R. Travassos et al., Exp. Mycol. 1:293-305, 1977) concanavalin A-reactive peptidorhamnomannan complexes, and their reactivity is probably due to the presence of acidic amino acids of low pK values rather than to glucuronic acid units.

  16. Distribution of Anionic Groups at the Cell Surface of Different Sporothrix schenckii Cell Types

    PubMed Central

    Benchimol, Marlene; de Souza, W.; Travassos, L. R.

    1979-01-01

    The distribution of anionic groups at the cell surface of yeastlike forms, hyphae, and conidia of Sporothrix schenckii was studied by staining with colloidal iron hydroxide and cationized ferritin. By using colloidal iron hydroxide it was shown that the external cell wall layer of one strain (strain 1099.18) could be resolved into two reactive sublayers and that these layers were present in many but not all cells of the same population. In contrast, most cells of another strain (strain 1099.12) were stained by colloidal iron hydroxide, but only one reactive layer was seen. Acidic layers of the yeastlike forms of the two strains were much thicker than those of conidia and hyphae. By the cationized ferritin staining procedure it was observed that the acidic layers of yeast forms sloughed off of cells, probably due to cell-cell or cell-medium attrition in shaken submerged cultures or to a process by which the outer layers detach from cells as they are replaced by newly synthesized ones. The colloidal iron hydroxide- and cationized ferritin-reactive cell surface layers of S. schenckii correspond to the previously described (L. R. Travassos et al., Exp. Mycol. 1:293-305, 1977) concanavalin A-reactive peptidorhamnomannan complexes, and their reactivity is probably due to the presence of acidic amino acids of low pK values rather than to glucuronic acid units. Images PMID:89092

  17. Pu Anion Exchange Process Intensification

    SciTech Connect

    Taylor-Pashow, K.

    2015-10-08

    This project seeks to improve the efficiency of the plutonium anion-exchange process for purifying Pu through the development of alternate ion-exchange media. The objective of the project in FY15 was to develop and test a porous foam monolith material that could serve as a replacement for the current anion-exchange resin, Reillex® HPQ, used at the Savannah River Site (SRS) for purifying Pu. The new material provides advantages in efficiency over the current resin by the elimination of diffusive mass transport through large granular resin beads. By replacing the large resin beads with a porous foam there is much more efficient contact between the Pu solution and the anion-exchange sites present on the material. Several samples of a polystyrene based foam grafted with poly(4-vinylpyridine) were prepared and the Pu sorption was tested in batch contact tests.

  18. Predicting As removal during metal hydroxide precipitation

    SciTech Connect

    McNeill, L.S.; Edwards, M.

    1997-01-01

    A simplified isotherm is described that can predict the extent of arsenate removal at drinking water utilities practicing coagulation or iron-manganese (Fe-Mn) removal. If all possible sources of particulate iron and aluminum hydroxide present in the system are accounted for, the model predicts arsenic (As) removal to within {+-}13 percent (90 percent confidence) for Fe coagulation at pH 6.5--8 and alum coagulation at pH < 7.6. Analysis of full-scale treatment data suggests that colloidal aluminum (Al) flocs with sorbed arsenate [As(V)] may pass through filters, thereby decreasing overall As removal efficiency. Thus, Al solubility and particle stability must be minimized to improve As removal. If stability and solubility of aluminum hydroxide flocs are not a problem, alum and Fe coagulants have nearly equal capacity for sorbing As(V). Survey results also demonstrate the importance of particulate As.

  19. Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Ferencz, Zs.; Szabados, M.; Varga, G.; Csendes, Z.; Kukovecz, Á.; Kónya, Z.; Carlson, S.; Sipos, P.; Pálinkó, I.

    2016-01-01

    A mechanochemical method (grinding the components without added water - dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution - wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure was also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic-inorganic nanocomposites: LDHs intercalated with amino acid anions.

  20. Pressure-induced decomposition of indium hydroxide.

    PubMed

    Gurlo, Aleksander; Dzivenko, Dmytro; Andrade, Miria; Riedel, Ralf; Lauterbach, Stefan; Kleebe, Hans-Joachim

    2010-09-15

    A static pressure-induced decomposition of indium hydroxide into metallic indium that takes place at ambient temperature is reported. The lattice parameter of c-In(OH)(3) decreased upon compression from 7.977(2) to approximately 7.45 A at 34 GPa, corresponding to a decrease in specific volume of approximately 18%. Fitting the second-order Birch-Murnaghan equation of state to the obtained compression data gave a bulk modulus of 99 +/- 3 GPa for c-In(OH)(3). The c-In(OH)(3) crystals with a size of approximately 100 nm are comminuted upon compression, as indicated by the grain-size reduction reflected in broadening of the diffraction reflections and the appearance of smaller (approximately 5 nm) incoherently oriented domains in TEM. The rapid decompression of compressed c-In(OH)(3) leads to partial decomposition of indium hydroxide into metallic indium, mainly as a result of localized stress gradients caused by relaxation of the highly disordered indium sublattice in indium hydroxide. This partial decomposition of indium hydroxide into metallic indium is irreversible, as confirmed by angle-dispersive X-ray diffraction, transmission electron microscopy imaging, Raman scattering, and FTIR spectroscopy. Recovered c-In(OH)(3) samples become completely black and nontransparent and show typical features of metals, i.e., a falling absorption in the 100-250 cm(-1) region accompanied by a featureless spectrum in the 250-2500 cm(-1) region in the Raman spectrum and Drude-like absorption of free electrons in the region of 4000-8000 cm(-1) in the FTIR spectrum. These features were not observed in the initial c-In(OH)(3), which is a typical white wide-band-gap semiconductor.

  1. UV-visible and (1)H-(15)N NMR spectroscopic studies of colorimetric thiosemicarbazide anion sensors.

    PubMed

    Farrugia, Kristina N; Makuc, Damjan; Podborska, Agnieszka; Szaciłowski, Konrad; Plavec, Janez; Magri, David C

    2015-02-14

    Four model thiosemicarbazide anion chemosensors containing three N-H bonds, substituted with phenyl and/or 4-nitrophenyl units, were synthesised and studied for their anion binding abilities with hydroxide, fluoride, acetate, dihydrogen phosphate and chloride. The anion binding properties were studied in DMSO and 9 : 1 DMSO-H2O by UV-visible absorption and (1)H/(13)C/(15)N NMR spectroscopic techniques and corroborated with DFT studies. Significant changes were observed in the UV-visible absorption spectra with all anions, except for chloride, accompanied by dramatic colour changes visible to the naked eye. These changes were determined to be due to the deprotonation of the central N-H proton and not due to hydrogen bonding based on (1)H/(15)N NMR titration studies with acetate in DMSO-d6-0.5% water. Direct evidence for deprotonation was confirmed by the disappearance of the central thiourea proton and the formation of acetic acid. DFT and charge distribution calculations suggest that for all four compounds the central N-H proton is the most acidic. Hence, the anion chemosensors operate by a deprotonation mechanism of the central N-H proton rather than by hydrogen bonding as is often reported. PMID:25451865

  2. Sodium hydroxide permethylation of heparin disaccharides.

    PubMed

    Heiss, Christian; Wang, Zhirui; Azadi, Parastoo

    2011-03-30

    Permethylation is a valuable and widely used tool for the mass spectrometry of carbohydrates, improving sensitivity and fragmentation and increasing the amount of information that can be obtained from tandem mass spectrometric experiments. Permethylation of most glycans is easily performed with sodium hydroxide and iodomethane in dimethyl sulfoxide (DMSO). However, permethylation has not been widely used in the mass spectrometry of glycosaminoglycan (GAG) oligosaccharides, partly because it has required the use of the difficult Hakomori method employing the methylsulfinylmethanide ('dimsyl') base, which has to be made in a tedious process. Additionally, the Hakomori method is not as effective as the sodium hydroxide method in making fully methylated derivatives. A further problem in the permethylation of highly sulfated oligosaccharides is their limited solubility in DMSO. This paper describes the use of the triethylammonium counterion to overcome this problem, as well as the application of the sodium hydroxide method to make permethylated heparin disaccharides and their workup to yield fully methylated disaccharides for electrospray ionization mass spectrometry. The ease, speed, and effectiveness of the described methodology should open up permethylation of GAG oligosaccharides to a wider circle of mass spectrometrists and enable them to develop further derivatization schemes in the effort to rapidly elucidate the structure of these important molecules. Permethylation may also provide new ways of separating GAG oligosaccharides in LC/MS, their increased hydrophobicity making them amenable for reversed-phase chromatography without the need for ion pairing reagents.

  3. A Novel Methodology to Synthesize Highly Conductive Anion Exchange Membranes

    NASA Astrophysics Data System (ADS)

    He, Yubin; Pan, Jiefeng; Wu, Liang; Zhu, Yuan; Ge, Xiaolin; Ran, Jin; Yang, Zhengjin; Xu, Tongwen

    2015-08-01

    Alkaline polyelectrolyte fuel cell now receives growing attention as a promising candidate to serve as the next generation energy-generating device by enabling the use of non-precious metal catalysts (silver, cobalt, nickel et al.). However, the development and application of alkaline polyelectrolyte fuel cell is still blocked by the poor hydroxide conductivity of anion exchange membranes. In order to solve this problem, we demonstrate a methodology for the preparation of highly OH- conductive anion exchange polyelectrolytes with good alkaline tolerance and excellent dimensional stability. Polymer backbones were grafted with flexible aliphatic chains containing two or three quaternized ammonium groups. The highly flexible and hydrophilic multi-functionalized side chains prefer to aggregate together to facilitate the formation of well-defined hydrophilic-hydrophobic microphase separation, which is crucial for the superior OH- conductivity of 69 mS/cm at room temperature. Besides, the as-prepared AEMs also exhibit excellent alkaline tolerance as well as improved dimensional stability due to their carefully designed polymer architecture, which provide new directions to pursue high performance AEMs and are promising to serve as a candidate for fuel cell technology.

  4. Interfacial material for solid oxide fuel cell

    DOEpatents

    Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

    1999-01-01

    Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

  5. Simultaneous enhancements of conductivity and stability for anion exchange membranes (AEMs) through precise structure design.

    PubMed

    Ran, Jin; Wu, Liang; Wei, Bing; Chen, Yaoyao; Xu, Tongwen

    2014-09-26

    Polymeric materials as anion exchange membranes (AEMs) play an essential role in the field of energy and environment. The achievement of high performance AEMs by the precise manipulation of macromolecular architecture remains a daunting challenge. Herein, we firstly report a novel rod-coil graft copolymer AEM, possessing rigid hydrophobic main chains and soft hydrophilic graft chains. The low graft density, which can alleviate the adverse influences of ionic graft chains on the main chains, was obtained by using the living polymerization technique. Consequently, the grafted ionic groups which result in the degradation of polymer backbone was decreased to a small degree. Moreover, the relatively long graft chains induced the nanophase separation between the hydrophobic polymer chains and hydrophilic graft chains, which creates a convenient pathway for high hydroxide ion mobility. Such an accurate molecular design simultaneously improves the hydroxide ion conductivity and alkaline stability as well as dimensional stability.

  6. Interfacial instabilities in vibrated fluids

    NASA Astrophysics Data System (ADS)

    Porter, Jeff; Laverón-Simavilla, Ana; Tinao Perez-Miravete, Ignacio; Fernandez Fraile, Jose Javier

    2016-07-01

    Vibrations induce a range of different interfacial phenomena in fluid systems depending on the frequency and orientation of the forcing. With gravity, (large) interfaces are approximately flat and there is a qualitative difference between vertical and horizontal forcing. Sufficient vertical forcing produces subharmonic standing waves (Faraday waves) that extend over the whole interface. Horizontal forcing can excite both localized and extended interfacial phenomena. The vibrating solid boundaries act as wavemakers to excite traveling waves (or sloshing modes at low frequencies) but they also drive evanescent bulk modes whose oscillatory pressure gradient can parametrically excite subharmonic surface waves like cross-waves. Depending on the magnitude of the damping and the aspect ratio of the container, these locally generated surfaces waves may interact in the interior resulting in temporal modulation and other complex dynamics. In the case where the interface separates two fluids of different density in, for example, a rectangular container, the mass transfer due to vertical motion near the endwalls requires a counterflow in the interior region that can lead to a Kelvin-Helmholtz type instability and a ``frozen wave" pattern. In microgravity, the dominance of surface forces favors non-flat equilibrium configurations and the distinction between vertical and horizontal applied forcing can be lost. Hysteresis and multiplicity of solutions are more common, especially in non-wetting systems where disconnected (partial) volumes of fluid can be established. Furthermore, the vibrational field contributes a dynamic pressure term that competes with surface tension to select the (time averaged) shape of the surface. These new (quasi-static) surface configurations, known as vibroequilibria, can differ substantially from the hydrostatic state. There is a tendency for the interface to orient perpendicular to the vibrational axis and, in some cases, a bulge or cavity is induced

  7. Interfacial behaviours of smart composites

    NASA Astrophysics Data System (ADS)

    Poon, Chi-Kin

    The success of conventional fiber reinforced composites (FRC) relies on the quality of bonding between fibers and matrix. A review of literatures shows that there is a lack of theoretical models and experimental findings on the interfacial behaviours of the SMA-composites. In the past, the operation limit as well as the ideal actuation condition of SMA inclusions could not be predicted accurately during the design stage and the SMA-composite structures may therefore suffer a potential risk of sudden failure due to overloading or over-actuation. The theoretical models developed in this research provide a study basis for the prediction of internal stresses and interfacial strength of the SMA-composites. Martensite volume fraction is considered as a critical parameter which determines the material properties and shape memory effect (SME) of the SMA inclusions. The proposed model reproduce the SMA behaviour inside a substrate, evolutions of martensite volume fraction and elastic modulus of SMA, and the internal stresses along the embedded length in different loading and actuation scenarios. The concepts of 'constant martensite volume fraction region (CMR)' and 'constant axial stress region (CASR)' are proposed to justify the desired SMA actuation. In addition, substantial improvement of the initial debond stress is predicted with the increase of the actuation temperature. The 'Optimum Actuation Condition (OAC)' that ensures the reinforcement of SMA composite but avoids the failure of composite interface due to over-actuation is also defined to optimize the application of SME in the composite structure within a safety actuation limit. A simplified OAC (SOAC) is also developed to provide an analytical solution of OAC and thus the ideal actuation temperature for achieving such specific actuation condition can be estimated more easily. Single fiber pullout test and finite element analysis (FEA) are employed to evaluate the interfacial behaviours and analyze the stress

  8. Interfacial adhesion: Theory and experiment

    NASA Technical Reports Server (NTRS)

    Ferrante, John; Bozzolo, Guillermo H.; Finley, Clarence W.; Banerjea, Amitava

    1988-01-01

    Adhesion, the binding of different materials at an interface, is of general interest to many branches of technology, e.g., microelectronics, tribology, manufacturing, construction, etc. However, there is a lack of fundamental understanding of such diverse interfaces. In addition, experimental techniques generally have practical objectives, such as the achievement of sufficient strength to sustain mechanical or thermal effects and/or have the proper electronic properties. In addition, the theoretical description of binding at interfaces is quite limited, and a proper data base for such theoretical analysis does not exist. This presentation will review both experimental and theoretical aspects of adhesion in nonpolymer materials. The objective will be to delineate the critical parameters needed, governing adhesion testing along with an outline of testing objectives. A distinction will be made between practical and fundamental objectives. Examples are given where interfacial bonding may govern experimental consideration. The present status of theory is presented along wiith recommendations for future progress and needs.

  9. Interfacial adhesion - Theory and experiment

    NASA Technical Reports Server (NTRS)

    Ferrante, John; Banerjea, Amitava; Bozzolo, Guillermo H.; Finley, Clarence W.

    1988-01-01

    Adhesion, the binding of different materials at an interface, is of general interest to many branches of technology, e.g., microelectronics, tribology, manufacturing, construction, etc. However, there is a lack of fundamental understanding of such diverse interfaces. In addition, experimental techniques generally have practical objectives, such as the achievement of sufficient strength to sustain mechanical or thermal effects and/or have the proper electronic properties. In addition, the theoretical description of binding at interfaces is quite limited, and a proper data base for such theoretical analysis does not exist. This presentation will review both experimental and theoretical aspects of adhesion in nonpolymer materials. The objective will be to delineate the critical parameters needed, governing adhesion testing along with an outline of testing objectives. A distinction will be made between practical and fundamental objectives. Examples are given where interfacial bonding may govern experimental consideration. The present status of theory is presented along with recommendations for future progress and needs.

  10. Interfacial instabilities and Kapitsa pendula

    NASA Astrophysics Data System (ADS)

    Krieger, Madison

    2015-11-01

    Determining the critera for onset and amplitude growth of instabilities is one of the central problems of fluid mechanics. We develop a parallel between the Kapitsa effect, in which a pendulum subject to high-frequency low-amplitude vibrations becomes stable in the inverted position, and interfaces separating fluids of different density. It has long been known that such interfaces can be stabilized by vibrations, even when the denser fluid is on top. We demonstrate that the stability diagram for these fluid interfaces is identical to the stability diagram for an appopriate Kapitsa pendulum. We expand the robust, ``dictionary''-type relationship between Kapitsa pendula and interfacial instabilities by considering the classical Rayleigh-Taylor, Kelvin-Helmholtz and Plateau instabilities, as well as less-canonical examples ranging in scale from the micron to the width of a galaxy.

  11. Interfacial Bioorthogonal Cross-Linking

    PubMed Central

    2015-01-01

    Described herein is interfacial bioorthogonal cross-linking, the use of bioorthogonal chemistry to create and pattern biomaterials through diffusion-controlled gelation at the liquid-gel interface. The basis is a rapid (k2 284000 M–1 s–1) reaction between strained trans-cyclooctene (TCO) and tetrazine (Tz) derivatives. Syringe delivery of Tz-functionalized hyaluronic acid (HA-Tz) to a bath of bis-TCO cross-linker instantly creates microspheres with a cross-linked shell through which bis-TCO diffuses freely to introduce further cross-linking at the interface. Tags can be introduced with 3D resolution without external triggers or templates. Water-filled hydrogel channels were prepared by simply reversing the order of addition. Prostate cancer cells encapsulated in the microspheres have 99% viability, proliferate readily, and form aggregated clusters. This process is projected to be useful in the fabrication of cell-instructive matrices for in vitro tissue models. PMID:25177528

  12. Layered double hydroxide stability. 1. Relative stabilities of layered double hydroxides and their simple counterparts

    NASA Technical Reports Server (NTRS)

    Boclair, J. W.; Braterman, P. S.

    1999-01-01

    Solutions containing di- and trivalent metal chlorides [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+; M(III) = Al3+, Fe3+] were titrated with NaOH to yield hydrotalcite-like layered double hydroxides (LDH), [[M(II)]1-x[M(III)]x(OH)2][Cl]x yH2O, by way of M(III) hydroxide/hydrous oxide intermediates. Analysis of the resultant titration curves yields nominal solubility constants for the LDH. The corresponding LDH stabilities are in the order Mg < Mn < Co approximately Ni < Zn for M(II) and Al < Fe for M(III). The stability of LDH relative to the separate metal hydroxides/hydrous oxides is discussed.

  13. Anion binding in biological systems

    NASA Astrophysics Data System (ADS)

    Feiters, Martin C.; Meyer-Klaucke, Wolfram; Kostenko, Alexander V.; Soldatov, Alexander V.; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Küpper, Frithjof C.; Hollenstein, Kaspar; Locher, Kaspar P.; Bevers, Loes E.; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

    2009-11-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L3 (2p3/2) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  14. Application of the SCC-DFTB method to hydroxide water clusters and aqueous hydroxide solutions.

    PubMed

    Choi, Tae Hoon; Liang, Ruibin; Maupin, C Mark; Voth, Gregory A

    2013-05-01

    The self-consistent charge density functional tight binding (SCC-DFTB) method has been applied to hydroxide water clusters and a hydroxide ion in bulk water. To determine the impact of various implementations of SCC-DFTB on the energetics and dynamics of a hydroxide ion in gas phase and condensed phase, the DFTB2, DFTB2-γ(h), DFTB2-γ(h)+gaus, DFTB3-diag, DFTB3-diag+gaus, DFTB3-Full+gaus, and DFTB3-3OB implementations have been tested. Energetic stabilities for small hydroxide clusters, OH(-)(H2O)n, where n = 4-7, are inconsistent with the results calculated with the B3LYP and second order Møller-Plesset (MP2) levels of ab initio theory. The condensed phase simulations, OH(-)(H2O)127, using the DFTB2, DFTB2-γ(h), DFTB2-γ(h)+gaus, DFTB3-diag, DFTB3-diag+gaus, DFTB3-Full+gaus and DFTB3-3OB methods are compared to Car-Parrinello molecular dynamics (CPMD) simulations using the BLYP functional. The SCC-DFTB method including a modified O-H repulsive potential and the third order correction (DFTB3-diag/Full+gaus) is shown to poorly reproduce the CPMD computational results, while the DFTB2 and DFTB2-γ(h) method somewhat more closely describe the structural and dynamical nature of the hydroxide ion in condensed phase. The DFTB3-3OB outperforms the MIO parameter set but is no more accurate than DFTB2. It is also shown that the overcoordinated water molecules lead to an incorrect bulk water density and result in unphysical water void formation. The results presented in this paper point to serious drawbacks for various DFTB extensions and corrections for a hydroxide ion in aqueous environments. PMID:23566052

  15. Sedimentation and deformation of an aqueous sodium hydroxide drop in vegetable oil

    NASA Astrophysics Data System (ADS)

    White, Andrew; Hyacinthe, Hyaquino; Ward, Thomas

    2013-11-01

    The addition of water droplets in fuels is known to provide benefits such as decreased Nitrous Oxide NOx emissions. Unfortunately the shelf life of a water-fuel emulsion is limited by the sedimentation rate of the water droplets. It is well known that adding surfactants can significantly slow the sedimentation rate due to the introduction of Marangoni stresses. In the case of a vegetable oil fuel, adding sodium hydroxide (NaOH) to the water droplets will produce surfactants through saponification in the form of sodium-carboxylate salts. Pendant drops of aqueous NaOH solutions with pH between 11 and 13 will be suspended in several oils such as corn, olive, canola and soybean oil in order to measure the interfacial tension. The change in interfacial tension with time will be used to estimate the surfactant concentration and the saponification rate. Then individual drops will be placed in the oils to observe the settling velocity and drop deformation. NSF CBET.

  16. Methanol-reforming reaction over copper-containing catalysts: the effects of anions and copper loading in the preparation of the catalysts by kneading method

    SciTech Connect

    Kobayashi, H.; Takezawa, N.; Minochi, C.

    1981-06-01

    Methanol-reforming reaction CH/sub 3/OH + H/sub 2/O = 3H/sub 2/ + CO/sub 2/ was carried out over copper-containing catalysts which were prepared from hydroxides of copper or from the hydroxide kneaded with various metal oxides. The specific activity (activity per weight of copper used) either of supported or support-free catalyst was markedly increased when the hydroxide was prepared from alkali solution with addition of copper salt solution at higher pH or when the weight percentage of copper on the support was decreased. However, other kinetic parameters such as activation energy and selectivity of the reaction were unaffected by the preparation of the catalyst unless copper chloride was employed as a starting material of the hydroxide preparation at lower pH. DTA, ir, XPS, AES and other chemical analyses of the catalysts revealed that hydroxide ion in the hydroxide precipitate prepared at lower pH exchanged in part with the anionic group of its starting material during the course of the preparation. The anion or its fragment was found to be strongly held on the surface and inhibited the reaction to a great extent. On the other hand, the anion held was markedly decreased when the catalyst was prepared at higher pH. This catalyst was found to be highly active for the title reaction. The surface areas of metallic copper were considerably increased when copper was kneaded with the support. This gave rise to the increase in the specific activity of the catalyst.

  17. Tunable Interfacial Thermal Conductance by Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Shen, Meng

    We study the mechanism of tunable heat transfer through interfaces between solids using a combination of non-equilibrium molecular dynamics simulation (NEMD), vibrational mode analysis and wave packet simulation. We investigate how heat transfer through interfaces is affected by factors including pressure, interfacial modulus, contact area and interfacial layer thickness, with an overreaching goal of developing fundamental knowledge that will allow one to tailor thermal properties of interfacial materials. The role of pressure and interfacial stiffness is unraveled by our studies on an epitaxial interface between two Lennard-Jones (LJ) crystals. The interfacial stiffness is varied by two different methods: (i) indirectly by applying pressure which due to anharmonic nature of bonding, increases interfacial stiffness, and (ii) directly by changing the interfacial bonding strength by varying the depth of the potential well of the LJ potential. When the interfacial bonding strength is low, quantitatively similar behavior to pressure tuning is observed when the interfacial thermal conductance is increased by directly varying the potential-well depth parameter of the LJ potential. By contrast, when the interfacial bonding strength is high, thermal conductance is almost pressure independent, and even slightly decreases with increasing pressure. This decrease can be explained by the change in overlap between the vibrational densities of states of the two crystalline materials. The role of contact area is studied by modeling structures comprised of Van der Waals junctions between single-walled nanotubes (SWCNT). Interfacial thermal conductance between SWCNTs is obtained from NEMD simulation as a function of crossing angle. In this case the junction conductance per unit area is essentially a constant. By contrast, interfacial thermal conductance between multiwalled carbon nanotubes (MWCNTs) is shown to increase with diameter of the nanotubes by recent experimental studies [1

  18. Tunable Interfacial Thermal Conductance by Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Shen, Meng

    We study the mechanism of tunable heat transfer through interfaces between solids using a combination of non-equilibrium molecular dynamics simulation (NEMD), vibrational mode analysis and wave packet simulation. We investigate how heat transfer through interfaces is affected by factors including pressure, interfacial modulus, contact area and interfacial layer thickness, with an overreaching goal of developing fundamental knowledge that will allow one to tailor thermal properties of interfacial materials. The role of pressure and interfacial stiffness is unraveled by our studies on an epitaxial interface between two Lennard-Jones (LJ) crystals. The interfacial stiffness is varied by two different methods: (i) indirectly by applying pressure which due to anharmonic nature of bonding, increases interfacial stiffness, and (ii) directly by changing the interfacial bonding strength by varying the depth of the potential well of the LJ potential. When the interfacial bonding strength is low, quantitatively similar behavior to pressure tuning is observed when the interfacial thermal conductance is increased by directly varying the potential-well depth parameter of the LJ potential. By contrast, when the interfacial bonding strength is high, thermal conductance is almost pressure independent, and even slightly decreases with increasing pressure. This decrease can be explained by the change in overlap between the vibrational densities of states of the two crystalline materials. The role of contact area is studied by modeling structures comprised of Van der Waals junctions between single-walled nanotubes (SWCNT). Interfacial thermal conductance between SWCNTs is obtained from NEMD simulation as a function of crossing angle. In this case the junction conductance per unit area is essentially a constant. By contrast, interfacial thermal conductance between multiwalled carbon nanotubes (MWCNTs) is shown to increase with diameter of the nanotubes by recent experimental studies [1

  19. Interfacial tension of aluminum in cryolite melts

    NASA Astrophysics Data System (ADS)

    Utigard, T.; Toguri, J. M.

    1985-06-01

    The interfacial tension between aluminum and cryolite melts containing different salt additions has been measured based on a combination of the sessile drop and X-ray radiographie technique. A computer program was used to calculate the interfacial tension from approximately twenty randomly measured coordinate points of the drop profile. Aluminum and salt mixtures containing different amounts of Na3AlF6, A1F3, NaF, A12O3, CaF2, KF, LiF, and NaCl were melted in a graphite or alumina crucible in a graphite resistor furnace under an argon atmosphere. The interfacial tension was found to be strongly dependent on the NaF/AlF3 ratio. At the cryolite composition the interfacial tension was 481 mN/m at 1304 K, while it was 650 mN/m when the NaF/AlF3 ratio was equal to 1.5. The change in interfacial tension with composition is explained by sodium enrichment of the Al/melt interface. Additions of A12O3 increased the interfacial tension for a given NaF/AlF3 ratio. KF was found to be surface active, while CaF2, LiF, and NaCl slightly increased the interfacial tension by decreasing the sodium activity.

  20. TREATMENT FOR IMPROVING THE OPERATION OF STRONG BASE ANION EXCHANGE RESINS

    DOEpatents

    Stevenson, P.C.

    1960-11-29

    A process is offered for improving quaternary ammonium type strongly basic anion exchange resins so that centain zinc and cadmium residues, which normally stick to and "poison" this type of resin, can be removed by elution. Specifically, the resin as obtained commercially is treated with an aqueous solution of sodium hydroxide of about 1 to 4 M concentration by heating therein and periodically adding small amounts of oxidizing agent selected from hydrogen peroxide, sodium peroxide and hypochlorite. Zinc and cadmium values may then be adsorbed onto the resin from a 0.1 to 3 M HCl and thereafter eluted therefrom with very dilute HCl solutions.

  1. Solvent Processable Tetraalkylammonium-Functionalized Polyethylene for Use as an Alkaline Anion Exchange Membrane

    SciTech Connect

    Kostalik, IV, Henry A.; Clark, Timothy J.; Robertson, Nicholas J.; Mutolo, Paul F.; Longo, Julie M.; Abruña, Héctor D.; Coates, Geoffrey W.

    2010-08-02

    We report the synthesis of a solvent processable, tetraalkylammonium-functionalized polyethylene for use as an alkaline anion exchange membrane (AAEM). The membranes are insoluble in both pure water and aqueous methanol (50 vol % water) at 50 °C but exhibit excellent solubility in a variety of other aqueous alcohols (e.g., 5 wt % AAEM in aqueous n-propanol, 50 vol % water). These solubility characteristics extend the potential utility of this system for use as both an AAEM and ionomer electrode material from a single polymer composition. The AAEMs generated are mechanically strong and exhibit high hydroxide and carbonate conductivities.

  2. Cu-Ce-O mixed oxides from Ce-containing layered double hydroxide precursors: Controllable preparation and catalytic performance

    NASA Astrophysics Data System (ADS)

    Chang, Zheng; Zhao, Na; Liu, Junfeng; Li, Feng; Evans, David G.; Duan, Xue; Forano, Claude; de Roy, Marie

    2011-12-01

    Cu/Zn/Al layered double hydroxide (LDH) precursors have been synthesized using an anion exchange method with anionic Ce complexes containing the dipicolinate (pyridine-2,6-dicarboxylate) ligand. Cu-Ce-O mixed oxides were obtained by calcination of the Ce-containing LDHs. The materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, and low temperature N 2 adsorption/desorption measurements. The results reveal that the inclusion of Ce has a significant effect on the specific surface area, pore structure, and chemical state of Cu in the resulting Cu-Ce-O mixed metal oxides. The resulting changes in composition and structure, particularly the interactions between Cu and Ce centers, significantly enhance the activity of the Ce-containing materials as catalysts for the oxidation of phenol by hydrogen peroxide.

  3. Anions dramatically enhance proton transfer through aqueous interfaces

    PubMed Central

    Mishra, Himanshu; Enami, Shinichi; Nielsen, Robert J.; Hoffmann, Michael R.; Goddard, William A.; Colussi, Agustín J.

    2012-01-01

    Proton transfer (PT) through and across aqueous interfaces is a fundamental process in chemistry and biology. Notwithstanding its importance, it is not generally realized that interfacial PT is quite different from conventional PT in bulk water. Here we show that, in contrast with the behavior of strong nitric acid in aqueous solution, gas-phase HNO3 does not dissociate upon collision with the surface of water unless a few ions (> 1 per 106 H2O) are present. By applying online electrospray ionization mass spectrometry to monitor in situ the surface of aqueous jets exposed to HNO3(g) beams we found that production increases dramatically on > 30-μM inert electrolyte solutions. We also performed quantum mechanical calculations confirming that the sizable barrier hindering HNO3 dissociation on the surface of small water clusters is drastically lowered in the presence of anions. Anions electrostatically assist in drawing the proton away from lingering outside the cluster, whose incorporation is hampered by the energetic cost of opening a cavity therein. Present results provide both direct experimental evidence and mechanistic insights on the counterintuitive slowness of PT at water-hydrophobe boundaries and its remarkable sensitivity to electrostatic effects. PMID:22689964

  4. Molecular modeling of hydrotalcite structure intercalated with transition metal oxide anions: CrO4(2-) and VO4(3-).

    PubMed

    Murthy, Vinuthaa; Smith, Howard D; Zhang, Hong; Smith, Sean C

    2011-11-24

    Molecular dynamics (MD) simulations are used to study the interlayer structure, hydrogen bonding, and energetics of hydration of Mg/Al (2:1 and 4:1) layered double hydroxide (LDH) or hydrotalcite (HT) intercalated with oxymetal anions, CrO(4)(2-), and VO(4)(3-). The ab initio forcefield COMPASS is employed for the simulations. The charge on the oxymetal anions is determined by quantum mechanical density functional theory. The structural behavior of the oxymetal anions in LDH directly relates to the energetic relationships, with electrostatic and H-bonding interactions between the anions, hydroxide sites of the metal hydroxide layers, and the interlayer water molecules. Distinct minima in the hydration energy indicate the presence of energetically well-defined structural states with specific water content. The experimentally identified variability in the retention of the CrO(4)(2-) and VO(4)(3-) is well reflected in the calculations and self-diffusion coefficients obtained from the simulations give insight into the mobility of the intercalated species.

  5. Ion exchange polymers for anion separations

    DOEpatents

    Jarvinen, G.D.; Marsh, S.F.; Bartsch, R.A.

    1997-09-23

    Anion exchange resins including at least two positively charged sites and a well-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

  6. Ion exchange polymers for anion separations

    DOEpatents

    Jarvinen, Gordon D.; Marsh, S. Fredric; Bartsch, Richard A.

    1997-01-01

    Anion exchange resins including at least two positively charged sites and a ell-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

  7. Infrared band intensities in ammonium hydroxide and ammonium salts

    NASA Technical Reports Server (NTRS)

    Sethna, P. P.; Downing, H. D.; Pinkley, L. W.; Williams, D.

    1978-01-01

    We have applied Kramers-Kronig analysis to reflection spectra to determine the optical constants of ammonium hydroxide and of aqueous solutions of ammonium chloride and bromide. From considerations of the absorption indices k(nu) we conclude that ammonium hydroxide consists of a solution of NH3 in water, in which NH3 molecules are hydrogen bonded to neighboring water molecules. The spectrum of ammonium hydroxide differs from the spectra of ammonium salts, in which bands characteristic of NH4(+) ions are prominent. The existence of ammonium hydroxide as an aerosol in planetary atmospheres is briefly discussed

  8. The alpha-form of the hydroxides of bivalent metals

    NASA Technical Reports Server (NTRS)

    Feitknecht, W.

    1984-01-01

    X-ray analyses were made of the hydroxides of the bivalent metals. The freshly pptd. hydroxide is usually in the alpha-form, which on standing is converted to another form or other forms. The alpha and c grating dimensions of the alpha-form and the C6-type of Co, Zn, C, Co-Zn and Ni-Zn hydroxides are tabulated. Ni hydroxide does not exhibit an alpha-form. The alpha-Co(OH)2, the blue form, is stabilized by sugar or by the higher alcohols: these compounds do not stabilize alpha-Zn(OH)2.

  9. Photoactive oriented films of layered double hydroxides.

    PubMed

    Lang, Kamil; Kubát, Pavel; Mosinger, Jirí; Bujdák, Juraj; Hof, Martin; Janda, Pavel; Sýkora, Jan; Iyi, Nobuo

    2008-08-14

    The treatment of nano-ordered oriented films of layered double hydroxide (LDH) with dodecyl sulfate increased the interlayer distance from 0.4 to 1.96 nm, which allowed the intercalation of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS). The re-stacking of separated layers and the rebuilding of crystals oriented parallel to the surface of quartz slides was confirmed by X-ray diffraction and atomic force microscopy. The hybrid films contained homogeneously distributed porphyrin molecules with preserved photophysical properties such as fluorescence, triplet state formation, and energy transfer, thus forming singlet oxygen.

  10. Selection and evaluation of adsorbents for the removal of anionic surfactants from laundry rinsing water.

    PubMed

    Schouten, Natasja; van der Ham, Louis G J; Euverink, Gert-Jan W; de Haan, André B

    2007-10-01

    Low-cost adsorbents were tested to remove anionic surfactants from laundry rinsing water to allow re-use of water. Adsorbents were selected corresponding to the different surfactant adsorption mechanisms. Equilibrium adsorption studies of linear alkyl benzene sulfonate (LAS) show that ionic interaction results in a high maximum adsorption capacity on positively charged adsorbents of 0.6-1.7 gLAS/g. Non-ionic interactions, such as hydrophobic interactions of LAS with non-ionic resins or activated carbons, result in a lower adsorption capacity of 0.02-0.6 gLAS/g. Negatively charged materials, such as cation exchange resins or bentonite clay, have negligible adsorption capacities for LAS. Similar results are obtained for alpha olefin sulfonate (AOS). Cost comparison of different adsorbents shows that an inorganic anion exchange material (layered double hydroxide) and activated carbons are the most cost-effective materials in terms of the amount of surfactant adsorbed per dollar worth of adsorbent.

  11. Acrylate intercalation and in situ polymerization in iron-, cobalt-, or manganese-substituted nickel hydroxides.

    PubMed

    Vaysse, C; Guerlou-Demourgues, L; Duguet, E; Delmas, C

    2003-07-28

    A chimie douce route based on successive redox and exchange reactions has allowed us to prepare new hybrid organic-inorganic materials, composed of polyacrylate macromolecules intercalated into layered double hydroxides (LDHs), deriving from Ni(OH)(2). Monomer intercalation and in situ polymerization mechanisms have appeared to be strongly dependent upon the nature of the substituting cation in the slabs. In the case of iron-based LDHs, a phase containing acrylate monomeric intercalates has been isolated and identified by X-ray diffraction and infrared spectroscopy. Second, interslab free-radical polymerization of acrylate anions has been successfully initiated using potassium persulfate. In cobalt- or manganese-based LDHs, one-step polymerization has been observed, leading directly to a material containing polyacrylate intercalate. PMID:12870945

  12. Methotrexate intercalated layered double hydroxides with the mediation of surfactants: Mechanism exploration and bioassay study.

    PubMed

    Dai, Chao-Fan; Tian, De-Ying; Li, Shu-Ping; Li, Xiao-Dong

    2015-12-01

    Methotrexatum intercalated layered double hydroxides (MTX/LDHs) hybrids were synthesized by the co-precipitation method and three kinds of nonionic surfactants with different hydrocarbon chain lengths were used. The resulting hybrids were then characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM). XRD and FTIR investigations manifest the successful intercalation of MTX anions into the interlayer of LDHs. TEM graphs indicate that the morphology of the hybrids changes with the variation of the chain length of the surfactants, i.e., the particles synthesized using polyethylene glycol (PEG-7) present regular disc morphology with good monodispersity, while samples with the mediation of alkyl polyglycoside (APG-14) are heavily aggregated and samples with the addition of polyvinylpyrrolidone (PVP-10) exhibit irregular branches. Furthermore, the release and bioassay experiments show that monodisperse MTX/LDHs present good controlled-release and are more efficient in the suppression of the tumor cells. PMID:26354264

  13. Mechanism of formation of magnetite from ferrous hydroxide in aqueous corrosion processes

    NASA Astrophysics Data System (ADS)

    Olowe, A. A.; Rezel, D.; Génin, J. M. R.

    1989-03-01

    The stoichiometric conditions for the formation of ferrous hydroxide Fe(OH)2, by mixing Fe2+ ions with caustic soda NaOH, leads by oxidation to magnetite, irrelevant of the foreign anions, e.g. Cl- or SO4 2-, as demonstrated from Mössbauer spectroscopy. The electrochemical potential Eh and pH value of the initial conditions correspond to the drastic change from basic to acidic medium, observed when varying the initial Fe2+/OH- ratio. Mössbauer analysis of the end products of oxidation at various temperatures shows that magnetite is only obtained at stoichiometry at very low temperature, but extends off stoichiometry at higher temperatures. The mechanism of formation of magnetite through an intermediate compound is discussed.

  14. Methotrexate intercalated layered double hydroxides with the mediation of surfactants: Mechanism exploration and bioassay study.

    PubMed

    Dai, Chao-Fan; Tian, De-Ying; Li, Shu-Ping; Li, Xiao-Dong

    2015-12-01

    Methotrexatum intercalated layered double hydroxides (MTX/LDHs) hybrids were synthesized by the co-precipitation method and three kinds of nonionic surfactants with different hydrocarbon chain lengths were used. The resulting hybrids were then characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM). XRD and FTIR investigations manifest the successful intercalation of MTX anions into the interlayer of LDHs. TEM graphs indicate that the morphology of the hybrids changes with the variation of the chain length of the surfactants, i.e., the particles synthesized using polyethylene glycol (PEG-7) present regular disc morphology with good monodispersity, while samples with the mediation of alkyl polyglycoside (APG-14) are heavily aggregated and samples with the addition of polyvinylpyrrolidone (PVP-10) exhibit irregular branches. Furthermore, the release and bioassay experiments show that monodisperse MTX/LDHs present good controlled-release and are more efficient in the suppression of the tumor cells.

  15. Platelets to rings: Influence of sodium dodecyl sulfate on Zn-Al layered double hydroxide morphology

    NASA Astrophysics Data System (ADS)

    Yilmaz, Ceren; Unal, Ugur; Yagci Acar, Havva

    2012-03-01

    In the current study, influence of sodium dodecyl sulfate (SDS) on the crystallization of Zn-Al layered double hydroxide (LDH) was investigated. Depending on the SDS concentration coral-like and for the first time ring-like morphologies were obtained in a urea-hydrolysis method. It was revealed that the surfactant level in the starting solution plays an important role in the morphology. Concentration of surfactant equal to or above the anion exchange capacity of the LDH is influential in creating different morphologies. Another important parameter was the critical micelle concentration (CMC) of the surfactant. Surfactant concentrations well above CMC value resulted in ring-like structures. The crystallization mechanism was discussed.

  16. The anion-binding polyanion: a molecular cobalt vanadium oxide with anion-sensitive visual response.

    PubMed

    Seliverstov, Andrey; Forster, Johannes; Heiland, Magdalena; Unfried, Johannes; Streb, Carsten

    2014-07-25

    An anionic molecular cobalt vanadium oxide cluster, (n-Bu4N)3[Co(AcO)V4O12] and its use as anion binding site is reported. Cluster formation is controlled by an anion-dependent dynamic solution equilibrium. Reversible anion binding in solution leads to significant spectral changes, allowing the ratiometric optical detection of the anion concentration in situ, even under harsh thermal conditions (T = 90 °C). Comparative studies showed that the spectral response is dependent on the type of anion so that carboxylates, weakly coordinating anions and halides can be distinguished.

  17. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles.

  18. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles. PMID:16430253

  19. Anion-induced urea deprotonation.

    PubMed

    Boiocchi, Massimo; Del Boca, Laura; Esteban-Gómez, David; Fabbrizzi, Luigi; Licchelli, Maurizio; Monzani, Enrico

    2005-05-01

    The urea-based receptor 1 (1-(7-nitrobenzo[1,2,5]oxadiazol-4-yl)-3-(4-nitrophenyl)urea, L--H), interacts with X- ions in MeCN, according to two consecutive steps: 1) formation of a hydrogen-bond complex [L--H...X]-; 2) deprotonation of L--H to give L- and [HX2]-, as shown by spectrophotometric and 1H NMR titration experiments. Step 2) takes place with more basic anions (fluoride, carboxylates, dihydrogenphosphate), while less basic anions (Cl-, NO2-, NO3-) do not induce proton transfer. On crystallisation from a solution containing L--H and excess Bu4NF, the tetrabutylammonium salt of the deprotonated urea derivative (Bu4N[L]) was isolated and its crystal and molecular structure determined. PMID:15770711

  20. Anion Solvation in Carbonate Electrolytes

    SciTech Connect

    Zhang, Zhengcheng

    2015-11-16

    With the correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. As of now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. As a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate, PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.

  1. Physicochemically functional ultrathin films by interfacial polymerization

    DOEpatents

    Lonsdale, H.K.; Babcock, W.C.; Friensen, D.T.; Smith, K.L.; Johnson, B.M.; Wamser, C.C.

    1990-08-14

    Interfacially-polymerized ultrathin films containing physicochemically functional groups are disclosed, both with and without supports. Various applications are disclosed, including membrane electrodes, selective membranes and sorbents, biocompatible materials, targeted drug delivery, and narrow band optical absorbers. 3 figs.

  2. Physicochemically functional ultrathin films by interfacial polymerization

    DOEpatents

    Lonsdale, Harold K.; Babcock, Walter C.; Friensen, Dwayne T.; Smith, Kelly L.; Johnson, Bruce M.; Wamser, Carl C.

    1990-01-01

    Interfacially-polymerized ultrathin films containing physicochemically functional groups are disclosed, both with and without supports. Various applications are disclsoed, including membrane electrodes, selective membranes and sorbents, biocompatible materials, targeted drug delivery, and narrow band optical absorbers.

  3. Aza compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li.sup.+ ion in alkali metal batteries.

  4. Aza compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.Q.; McBreen, J.

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li{sup +} ion in alkali metal batteries. 3 figs.

  5. Direct observation of grafting interlayer phosphate in Mg/Al layered double hydroxides

    SciTech Connect

    Shimamura, Akihiro; Kanezaki, Eiji; Jones, Mark I.; Metson, James B.

    2012-02-15

    The grafting of interlayer phosphate in synthetic Mg/Al layered double hydroxides with interlayer hydrogen phosphate (LDH-HPO{sub 4}) has been studied by XRD, TG/DTA, FT-IR, XPS and XANES. The basal spacing of crystalline LDH-HPO{sub 4} decreases in two stages with increasing temperature, from 1.06 nm to 0.82 nm at 333 K in the first transition, and to 0.722 nm at 453 K in the second. The first stage occurs due to the loss of interlayer water and rearrangement of the interlayer HPO{sub 4}{sup 2-}. In the second transition, the interlayer phosphate is grafted to the layer by the formation of direct bonding to metal cations in the layer, accompanied by a change in polytype of the crystalline structure. The grafted phosphate becomes immobilized and cannot be removed by anion-exchange with 1-octanesulfonate. The LDH is amorphous at 743 K but decomposes to Mg{sub 3}(PO{sub 4}){sub 2}, AlPO{sub 4}, MgO and MgAl{sub 2}O{sub 4} after heated to 1273 K. - Graphical abstract: The cross section of the synthetic Mg, Al layered double hydroxides in Phase 1, with interlayer hydrogen phosphate Phase 2, and with grafted phosphate, Phase 3. Highlights: Black-Right-Pointing-Pointer The grafting of hydrogen phosphate intercalated Mg/Al-LDH has been studied. Black-Right-Pointing-Pointer The basal spacing of crystalline LDH-HPO{sub 4} decreases in two stages with increasing temperature. Black-Right-Pointing-Pointer The first decrease is due to loss of interlayer water, the second is attributed to phosphate grafting. Black-Right-Pointing-Pointer The grafted interlayer phosphate becomes immobilized and cannot be removed by anion-exchange.

  6. Intercalation and controlled release properties of vitamin C intercalated layered double hydroxide

    SciTech Connect

    Gao, Xiaorui; Lei, Lixu; O'Hare, Dermot; Xie, Juan; Gao, Pengran; Chang, Tao

    2013-07-15

    Two drug-inorganic composites involving vitamin C (VC) intercalated in Mg–Al and Mg–Fe layered double hydroxides (LDHs) have been synthesized by the calcination–rehydration (reconstruction) method. Powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), and UV–vis absorption spectroscopy indicate a successful intercalation of VC into the interlayer galleries of the LDH host. Studies of VC release from the LDHs in deionised water and in aqueous CO{sub 3}{sup 2−} solutions imply that Mg{sub 3}Al–VC LDH is a better controlled release system than Mg{sub 3}Fe–VC LDH. Analysis of the release profiles using a number of kinetic models suggests a solution-dependent release mechanism, and a diffusion-controlled deintercalation mechanism in deionised water, but an ion exchange process in CO{sub 3}{sup 2−} solution. - Graphical abstract: Vitamin C anions have been intercalated in the interlayer space of layered double hydroxide and released in CO{sub 3}{sup 2−} solution and deionised water. - Highlights: • Vitamin C intercalated Mg–Al and Mg–Fe layered double hydroxides were prepared. • Release property of vitamin C in aqueous CO{sub 3}{sup 2−} solution is better. • Avrami-Erofe’ev and first-order models provide better fit for release results. • Diffusion-controlled and ion exchange processes occur in deionised water. • An ion exchange process occurs in CO{sub 3}{sup 2−} solution.

  7. Electric Field Induced Interfacial Instabilities

    NASA Technical Reports Server (NTRS)

    Kusner, Robert E.; Min, Kyung Yang; Wu, Xiao-Lun; Onuki, Akira

    1996-01-01

    The study of the interface in a charge-free, nonpolar, critical and near-critical binary fluid in the presence of an externally applied electric field is presented. At sufficiently large fields, the interface between the two phases of the binary fluid should become unstable and exhibit an undulation with a predefined wavelength on the order of the capillary length. As the critical point is approached, this wavelength is reduced, potentially approaching length-scales such as the correlation length or critical nucleation radius. At this point the critical properties of the system may be affected. In zero gravity, the interface is unstable at all long wavelengths in the presence of a field applied across it. It is conjectured that this will cause the binary fluid to break up into domains small enough to be outside the instability condition. The resulting pattern formation, and the effects on the critical properties as the domains approach the correlation length are of acute interest. With direct observation, laser light scattering, and interferometry, the phenomena can be probed to gain further understanding of interfacial instabilities and the pattern formation which results, and dimensional crossover in critical systems as the critical fluctuations in a particular direction are suppressed by external forces.

  8. Interfacial adsorption in ternary alloys

    SciTech Connect

    Huang, C.; Cruz, M.O. de la; Voorhees, P.W.

    1999-11-26

    Interfaces of A-B-C ternary alloys decomposed into two and three phases are studied. The effect of the gradient energy coefficients {bar {kappa}}{sub II}, I = A, B, C, on the interface composition profiles of ternary alloys is examined. The adsorption of component C in ternary alloys is obtained numerically by finding steady-state solutions of the nonlinear Cahn-Hilliard equations and by solving the two Euler-Lagrange equations resulting from minimizing the interfacial energy, and analytically near the critical point. It is found that the solutions from both numerical methods are identical for a two-phase system. In symmetric ternary systems (equal interaction energy between each pair of components) with a minority component C, the gradient energy coefficient of C, {bar {kappa}}{sub CC}, can have a very strong influence on the degree of adsorption. In the {alpha} and {beta} two-phase regions, where {alpha} and {beta} are the phases rich in the majority components A and B, respectively, as {bar {kappa}}{sub CC} increases, the adsorption of the minority component C in the {alpha} and {beta} interfaces decreases. Near a critical point, however, the degree of adsorption of minority component C is independent of the gradient energy coefficient.

  9. Interfacial engineering for silica nanocapsules.

    PubMed

    Wibowo, David; Hui, Yue; Middelberg, Anton P J; Zhao, Chun-Xia

    2016-10-01

    Silica nanocapsules have attracted significant interest due to their core-shell hierarchical structure. The core domain allows the encapsulation of various functional components such as drugs, fluorescent and magnetic nanoparticles for applications in drug delivery, imaging and sensing, and the silica shell with its unique properties including biocompatibility, chemical and physical stability, and surface-chemistry tailorability provides a protection layer for the encapsulated cargo. Therefore, significant effort has been directed to synthesize silica nanocapsules with engineered properties, including size, composition and surface functionality, for various applications. This review provides a comprehensive overview of emerging methods for the manufacture of silica nanocapsules, with a special emphasis on different interfacial engineering strategies. The review starts with an introduction of various manufacturing approaches of silica nanocapsules highlighting surface engineering of the core template nanomaterials (solid nanoparticles, liquid droplets, and gas bubbles) using chemicals or biomolecules which are able to direct nucleation and growth of silica at the boundary of two-phase interfaces (solid-liquid, liquid-liquid, and gas-liquid). Next, surface functionalization of silica nanocapsules is presented. Furthermore, strategies and challenges of encapsulating active molecules (pre-loading and post-loading approaches) in these capsular systems are critically discussed. Finally, applications of silica nanocapsules in controlled release, imaging, and theranostics are reviewed. PMID:27522646

  10. Modeling interfacial fracture in Sierra.

    SciTech Connect

    Brown, Arthur A.; Ohashi, Yuki; Lu, Wei-Yang; Nelson, Stacy A. C.; Foulk, James W.,; Reedy, Earl David,; Austin, Kevin N.; Margolis, Stephen B.

    2013-09-01

    This report summarizes computational efforts to model interfacial fracture using cohesive zone models in the SIERRA/SolidMechanics (SIERRA/SM) finite element code. Cohesive surface elements were used to model crack initiation and propagation along predefined paths. Mesh convergence was observed with SIERRA/SM for numerous geometries. As the funding for this project came from the Advanced Simulation and Computing Verification and Validation (ASC V&V) focus area, considerable effort was spent performing verification and validation. Code verification was performed to compare code predictions to analytical solutions for simple three-element simulations as well as a higher-fidelity simulation of a double-cantilever beam. Parameter identification was conducted with Dakota using experimental results on asymmetric double-cantilever beam (ADCB) and end-notched-flexure (ENF) experiments conducted under Campaign-6 funding. Discretization convergence studies were also performed with respect to mesh size and time step and an optimization study was completed for mode II delamination using the ENF geometry. Throughout this verification process, numerous SIERRA/SM bugs were found and reported, all of which have been fixed, leading to over a 10-fold increase in convergence rates. Finally, mixed-mode flexure experiments were performed for validation. One of the unexplained issues encountered was material property variability for ostensibly the same composite material. Since the variability is not fully understood, it is difficult to accurately assess uncertainty when performing predictions.

  11. Synthesis of layered double hydroxide nanosheets by coprecipitation using a T-type microchannel reactor

    SciTech Connect

    Pang, Xiujiang; Sun, Meiyu; Ma, Xiuming; Hou, Wanguo

    2014-02-15

    The synthesis of Mg{sub 2}Al–NO{sub 3} layered double hydroxide (LDH) nanosheets by coprecipitation using a T-type microchannel reactor is reported. Aqueous LDH nanosheet dispersions were obtained. The LDH nanosheets were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy and particle size analysis, and the transmittance and viscosity of LDH nanosheet dispersions were examined. The two-dimensional LDH nanosheets consisted of 1–2 brucite-like layers and were stable for ca. 16 h at room temperature. In addition, the co-assembly between LDH nanosheets and dodecyl sulfate (DS) anions was carried out, and a DS intercalated LDH nanohybrid was obtained. To the best of our knowledge, this is the first report of LDH nanosheets being directly prepared in bulk aqueous solution. This simple, cheap method can provide naked LDH nanosheets in high quantities, which can be used as building blocks for functional materials. - Graphical abstract: Layered double hydroxide (LDH) nanosheets were synthesized by coprecipitation using a T-type microchannel reactor, and could be used as basic building blocks for LDH-based functional materials. Display Omitted - Highlights: • LDH nanosheets were synthesized by coprecipitation using a T-type microchannel reactor. • Naked LDH nanosheets were dispersed in aqueous media. • LDH nanosheets can be used as building blocks for functional materials.

  12. 3D Magnetically Ordered Open Supramolecular Architectures Based on Ferrimagnetic Cu/Adenine/Hydroxide Heptameric Wheels.

    PubMed

    Pérez-Aguirre, Rubén; Beobide, Garikoitz; Castillo, Oscar; de Pedro, Imanol; Luque, Antonio; Pérez-Yáñez, Sonia; Rodríguez Fernández, Jesús; Román, Pascual

    2016-08-01

    The present work provides two new examples of supramolecular metal-organic frameworks consisting of three-dimensional extended noncovalent assemblies of wheel-shaped heptanuclear [Cu7(μ-H2O)6(μ3-OH)6(μ-adeninato-κN3:κN9)6](2+) entities. The heptanuclear entity consists of a central [Cu(OH)6](4-) core connected to six additional copper(II) metal centers in a radial and planar arrangement through the hydroxides. It generates a wheel-shaped entity in which water molecules and μ-κN3:κN9 adeninato ligands bridge the peripheral copper atoms. The magnetic characterization indicates the central copper(II) center is anti-ferromagnetically coupled to external copper(II) centers, which are ferromagnetically coupled among them leading to an S = 5/2 ground state. The packing of these entities is sustained by π-π stacking interactions between the adenine nucleobases and by hydrogen bonds established among the hydroxide ligands, sulfate anions, and adenine nucleobases. The sum of both types of supramolecular interactions creates a rigid synthon that in combination with the rigidity of the heptameric entity generates an open supramolecular structure (40-50% of available space) in which additional sulfate and triethylammonium ions are located altogether with solvent molecules. These compounds represent an interesting example of materials combining both porosity and magnetic relevant features.

  13. Organo/layered double hydroxide nanohybrids used to remove non ionic pesticides.

    PubMed

    Chaara, D; Bruna, F; Ulibarri, M A; Draoui, K; Barriga, C; Pavlovic, I

    2011-11-30

    The preparation and characterization of organo/layered double hydroxide nanohybrids with dodecylsulfate and sebacate as interlayer anion were studied in detail. The aim of the modification of the layered double hydroxides (LDHs) was to change the hydrophilic character of the interlayer to hydrophobic to improve the ability of the nanohybrids to adsorb non-ionic pesticides such as alachlor and metolachlor from water. Adsorption tests were conducted on organo/LDHs using variable pH values, contact times and initial pesticide concentrations (adsorption isotherms) in order to identify the optimum conditions for the intended purpose. Adsorbents and adsorption products were characterized several physicochemical techniques. The adsorption test showed that a noticeable increase of the adsorption of the non-ionic herbicides was produced. Based on the results, the organo/LDHs could be good adsorbents to remove alachlor and metolachlor from water. Different organo/LDHs complexes were prepared by a mechanical mixture and by adsorption. The results show that HTSEB-based complex displays controlled release properties that reduce metolachlor leaching in soil columns compared to a technical product and the other formulations. The release was dependent on the nature of the adsorbent used to prepare the complexes. Thus, it can be concluded that organo/LDHs might act as suitable supports for the design of pesticide slow release formulations with the aim of reducing the adverse effects derived from rapid transport losses of the chemical once applied to soils. PMID:21978582

  14. Organo/layered double hydroxide nanohybrids used to remove non ionic pesticides.

    PubMed

    Chaara, D; Bruna, F; Ulibarri, M A; Draoui, K; Barriga, C; Pavlovic, I

    2011-11-30

    The preparation and characterization of organo/layered double hydroxide nanohybrids with dodecylsulfate and sebacate as interlayer anion were studied in detail. The aim of the modification of the layered double hydroxides (LDHs) was to change the hydrophilic character of the interlayer to hydrophobic to improve the ability of the nanohybrids to adsorb non-ionic pesticides such as alachlor and metolachlor from water. Adsorption tests were conducted on organo/LDHs using variable pH values, contact times and initial pesticide concentrations (adsorption isotherms) in order to identify the optimum conditions for the intended purpose. Adsorbents and adsorption products were characterized several physicochemical techniques. The adsorption test showed that a noticeable increase of the adsorption of the non-ionic herbicides was produced. Based on the results, the organo/LDHs could be good adsorbents to remove alachlor and metolachlor from water. Different organo/LDHs complexes were prepared by a mechanical mixture and by adsorption. The results show that HTSEB-based complex displays controlled release properties that reduce metolachlor leaching in soil columns compared to a technical product and the other formulations. The release was dependent on the nature of the adsorbent used to prepare the complexes. Thus, it can be concluded that organo/LDHs might act as suitable supports for the design of pesticide slow release formulations with the aim of reducing the adverse effects derived from rapid transport losses of the chemical once applied to soils.

  15. Synthesis and controlled release properties of 2,4-dichlorophenoxy acetate–zinc layered hydroxide nanohybrid

    SciTech Connect

    Bashi, Abbas M.; Hussein, Mohd Zobir; Zainal, Zulkarnain; Tichit, Didier

    2013-07-15

    Direct reaction of ZnO with 2,4-dichlorophenoxyacetic acid (24D) solutions of different concentrations allows obtaining new organic–inorganic nanohybrid materials formed by intercalation of 24D into interlayers of zinc layered hydroxide (ZLH). XRD patterns show a progressive evolution of the structure as 24D concentration increases. The nanohybrid obtained at higher 24D concentration (24D–ZLH(0.4)) reveals a well ordered layered structure with two different basal spacings at 25.2 Å and 24 Å. The FTIR spectrum showing the vibrations bands of the functional groups of 24D and of the ZLH confirms the intercalation. SEM images are in agreement with the structural evolution observed by XRD and reveal the ribbon morphology of the nanohybrids. The release studies of 24D showed a rapid release of 94% for the first 100 min governed by the pseudo-second order kinetic model. - Graphical abstract: The phenomenon indicates that the optical energy gap is enlarged with the increase of molar concentrations in 2,4-dichlorophenoxy acetate anion content into ZnO to create a ZLH–24D nanohybrid. - Highlights: • Nanohybrid was synthesized from 2,4-dichlorophenoxy acetate with-Zinc LHD, using wet chemistry. • Characterized using SEM, TEM, EDX, FTIR, XRD and TGA. • Ribbon-shaped 24D–Zn-layered hydroxide nanoparticles with (003) diffractions of 2.5 nm phase were synthesized.

  16. Synthesis of (cinnamate-zinc layered hydroxide) intercalation compound for sunscreen application

    PubMed Central

    2013-01-01

    Background Zinc layered hydroxide (ZLH) intercalated with cinnamate, an anionic form of cinnamic acid (CA), an efficient UVA and UVB absorber, have been synthesized by direct method using zinc oxide (ZnO) and cinnamic acid as the precursor. Results The resulting obtained intercalation compound, ZCA, showed a basal spacing of 23.9 Å as a result of cinnamate intercalated in a bilayer arrangement between the interlayer spaces of ZLH with estimated percentage loading of cinnamate of about 40.4 % w/w. The UV–vis absorption spectrum of the intercalation compound showed excellent UVA and UVB absorption ability. Retention of cinnamate in ZLH interlayers was tested against media usually came across with sunscreen usage to show low release over an extended period of time. MTT assay of the intercalation compound on human dermal fibroblast (HDF) cells showed cytotoxicity of ZCA to be concentration dependent and is overall less toxic than its precursor, ZnO. Conclusions (Cinnamate-zinc layered hydroxide) intercalation compound is suitable to be used as a safe and effective sunscreen with long UV protection effect. PMID:23383738

  17. 3D Magnetically Ordered Open Supramolecular Architectures Based on Ferrimagnetic Cu/Adenine/Hydroxide Heptameric Wheels.

    PubMed

    Pérez-Aguirre, Rubén; Beobide, Garikoitz; Castillo, Oscar; de Pedro, Imanol; Luque, Antonio; Pérez-Yáñez, Sonia; Rodríguez Fernández, Jesús; Román, Pascual

    2016-08-01

    The present work provides two new examples of supramolecular metal-organic frameworks consisting of three-dimensional extended noncovalent assemblies of wheel-shaped heptanuclear [Cu7(μ-H2O)6(μ3-OH)6(μ-adeninato-κN3:κN9)6](2+) entities. The heptanuclear entity consists of a central [Cu(OH)6](4-) core connected to six additional copper(II) metal centers in a radial and planar arrangement through the hydroxides. It generates a wheel-shaped entity in which water molecules and μ-κN3:κN9 adeninato ligands bridge the peripheral copper atoms. The magnetic characterization indicates the central copper(II) center is anti-ferromagnetically coupled to external copper(II) centers, which are ferromagnetically coupled among them leading to an S = 5/2 ground state. The packing of these entities is sustained by π-π stacking interactions between the adenine nucleobases and by hydrogen bonds established among the hydroxide ligands, sulfate anions, and adenine nucleobases. The sum of both types of supramolecular interactions creates a rigid synthon that in combination with the rigidity of the heptameric entity generates an open supramolecular structure (40-50% of available space) in which additional sulfate and triethylammonium ions are located altogether with solvent molecules. These compounds represent an interesting example of materials combining both porosity and magnetic relevant features. PMID:27409976

  18. Protons and Hydroxide Ions in Aqueous Systems.

    PubMed

    Agmon, Noam; Bakker, Huib J; Campen, R Kramer; Henchman, Richard H; Pohl, Peter; Roke, Sylvie; Thämer, Martin; Hassanali, Ali

    2016-07-13

    Understanding the structure and dynamics of water's constituent ions, proton and hydroxide, has been a subject of numerous experimental and theoretical studies over the last century. Besides their obvious importance in acid-base chemistry, these ions play an important role in numerous applications ranging from enzyme catalysis to environmental chemistry. Despite a long history of research, many fundamental issues regarding their properties continue to be an active area of research. Here, we provide a review of the experimental and theoretical advances made in the last several decades in understanding the structure, dynamics, and transport of the proton and hydroxide ions in different aqueous environments, ranging from water clusters to the bulk liquid and its interfaces with hydrophobic surfaces. The propensity of these ions to accumulate at hydrophobic surfaces has been a subject of intense debate, and we highlight the open issues and challenges in this area. Biological applications reviewed include proton transport along the hydration layer of various membranes and through channel proteins, problems that are at the core of cellular bioenergetics. PMID:27314430

  19. Protons and Hydroxide Ions in Aqueous Systems.

    PubMed

    Agmon, Noam; Bakker, Huib J; Campen, R Kramer; Henchman, Richard H; Pohl, Peter; Roke, Sylvie; Thämer, Martin; Hassanali, Ali

    2016-07-13

    Understanding the structure and dynamics of water's constituent ions, proton and hydroxide, has been a subject of numerous experimental and theoretical studies over the last century. Besides their obvious importance in acid-base chemistry, these ions play an important role in numerous applications ranging from enzyme catalysis to environmental chemistry. Despite a long history of research, many fundamental issues regarding their properties continue to be an active area of research. Here, we provide a review of the experimental and theoretical advances made in the last several decades in understanding the structure, dynamics, and transport of the proton and hydroxide ions in different aqueous environments, ranging from water clusters to the bulk liquid and its interfaces with hydrophobic surfaces. The propensity of these ions to accumulate at hydrophobic surfaces has been a subject of intense debate, and we highlight the open issues and challenges in this area. Biological applications reviewed include proton transport along the hydration layer of various membranes and through channel proteins, problems that are at the core of cellular bioenergetics.

  20. Interfacial area transport in bubbly flow

    SciTech Connect

    Ishii, M.; Wu, Q.; Revankar, S.T.

    1997-12-31

    In order to close the two-fluid model for two-phase flow analyses, the interfacial area concentration needs to be modeled as a constitutive relation. In this study, the focus was on the investigation of the interfacial area concentration transport phenomena, both theoretically and experimentally. The interfacial area concentration transport equation for air-water bubbly up-flow in a vertical pipe was developed, and the models for the source and sink terms were provided. The necessary parameters for the experimental studies were identified, including the local time-averaged void fraction, interfacial area concentration, bubble interfacial velocity, liquid velocity and turbulent intensity. Experiments were performed with air-water mixture at atmospheric pressure. Double-sensor conductivity probe and hot-film probe were employed to measure the identified parameters. With these experimental data, the preliminary model evaluation was carried out for the simplest form of the developed interfacial area transport equation, i.e., the one-dimensional transport equation.

  1. Conformational NMR Study of Bistriazolyl Anion Receptors.

    PubMed

    Makuc, Damjan; Merckx, Tamara; Dehaen, Wim; Plavec, Janez

    2016-01-01

    Conformational features of pyridine- and pyrimidine-based bistriazolyl anion receptors dissolved in acetonitrile-d3 were assessed by multidimensional, heteronuclear NMR spectroscopy. NOESY correlation signals suggested preorganization of both host molecules in solution in the absence of anions. In addition, only a single set of signals was observed in the 1H NMR spectra, which suggested a symmetrical conformation of anion receptors or their conformational exchange that is fast on the NMR time-scale. Furthermore, the predominant conformations of the pyridine- and pyrimidine-based anion receptors are preserved upon addition of chloride, bromide, and acetate anions. Chemical shift changes observed upon addition of anions showed that the NH (thio)urea and triazole protons are involved in anion-receptor interactions through hydrogen bonding. PMID:27640375

  2. Gel for Simultaneous Chemical Imaging of Anionic and Cationic Solutes Using Diffusive Gradients in Thin Films

    PubMed Central

    2013-01-01

    We report on a novel gel based on diffusive gradients in thin films (DGT) for the simultaneous measurement of cations and anions and its suitability for high resolution chemical imaging by using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The new high resolution mixed binding gel (HR-MBG) is based on zirconium-hydroxide and suspended particulate reagent-iminodiacetate (SPR-IDA) as resin materials which are embedded in an ether-based urethane polymer hydrogel. The use of this polymer hydrogel material allows the production of ultrathin, highly stable and tear-proof resin gel layers with superior handling properties compared to existing ultrathin polyacrylamide gels. The gel was characterized regarding its uptake kinetics, the anion and cation capacities, and the effects of pH, ionic strength, and aging on the performance of the HR-MBG. Our results demonstrate the capability of this novel gel for concomitant sampling of anions and cations. The suitability of this new gel type for DGT chemical imaging at submm spatial resolution in soils using LA-ICPMS is shown. 2D images of P, As, Co, Cu, Mn, and Zn distributions around roots of Zea mays L. demonstrate the new opportunities offered by the HR-MBG for high-resolution mapping of solute dynamics in soil and sediment hotspots, such as the rhizosphere, by simultaneous observation of anionic and cationic solute species. PMID:24256092

  3. Gel for simultaneous chemical imaging of anionic and cationic solutes using diffusive gradients in thin films.

    PubMed

    Kreuzeder, Andreas; Santner, Jakob; Prohaska, Thomas; Wenzel, Walter W

    2013-12-17

    We report on a novel gel based on diffusive gradients in thin films (DGT) for the simultaneous measurement of cations and anions and its suitability for high resolution chemical imaging by using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The new high resolution mixed binding gel (HR-MBG) is based on zirconium-hydroxide and suspended particulate reagent-iminodiacetate (SPR-IDA) as resin materials which are embedded in an ether-based urethane polymer hydrogel. The use of this polymer hydrogel material allows the production of ultrathin, highly stable and tear-proof resin gel layers with superior handling properties compared to existing ultrathin polyacrylamide gels. The gel was characterized regarding its uptake kinetics, the anion and cation capacities, and the effects of pH, ionic strength, and aging on the performance of the HR-MBG. Our results demonstrate the capability of this novel gel for concomitant sampling of anions and cations. The suitability of this new gel type for DGT chemical imaging at submm spatial resolution in soils using LA-ICPMS is shown. 2D images of P, As, Co, Cu, Mn, and Zn distributions around roots of Zea mays L. demonstrate the new opportunities offered by the HR-MBG for high-resolution mapping of solute dynamics in soil and sediment hotspots, such as the rhizosphere, by simultaneous observation of anionic and cationic solute species.

  4. Gel for simultaneous chemical imaging of anionic and cationic solutes using diffusive gradients in thin films.

    PubMed

    Kreuzeder, Andreas; Santner, Jakob; Prohaska, Thomas; Wenzel, Walter W

    2013-12-17

    We report on a novel gel based on diffusive gradients in thin films (DGT) for the simultaneous measurement of cations and anions and its suitability for high resolution chemical imaging by using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The new high resolution mixed binding gel (HR-MBG) is based on zirconium-hydroxide and suspended particulate reagent-iminodiacetate (SPR-IDA) as resin materials which are embedded in an ether-based urethane polymer hydrogel. The use of this polymer hydrogel material allows the production of ultrathin, highly stable and tear-proof resin gel layers with superior handling properties compared to existing ultrathin polyacrylamide gels. The gel was characterized regarding its uptake kinetics, the anion and cation capacities, and the effects of pH, ionic strength, and aging on the performance of the HR-MBG. Our results demonstrate the capability of this novel gel for concomitant sampling of anions and cations. The suitability of this new gel type for DGT chemical imaging at submm spatial resolution in soils using LA-ICPMS is shown. 2D images of P, As, Co, Cu, Mn, and Zn distributions around roots of Zea mays L. demonstrate the new opportunities offered by the HR-MBG for high-resolution mapping of solute dynamics in soil and sediment hotspots, such as the rhizosphere, by simultaneous observation of anionic and cationic solute species. PMID:24256092

  5. Analysis of carbohydrates by anion exchange chromatography and mass spectrometry.

    PubMed

    Bruggink, Cees; Maurer, Rolf; Herrmann, Heiko; Cavalli, Silvano; Hoefler, Frank

    2005-08-26

    A versatile liquid chromatographic platform has been developed for analysing underivatized carbohydrates using high performance anion exchange chromatography (HPAEC) followed by an inert PEEK splitter that splits the effluent to the integrated pulsed amperometric detector (IPAD) and to an on-line single quadrupole mass spectrometer (MS). Common eluents for HPAEC such as sodium hydroxide and sodium acetate are beneficial for the amperometric detection but not compatible with electrospray ionisation (ESI). Therefore a membrane-desalting device was installed after the splitter and prior to the ESI interface converting sodium hydroxide into water and sodium acetate into acetic acid. To enhance the sensitivity for the MS detection, 0.5 mmol/l lithium chloride was added after the membrane desalter to form lithium adducts of the carbohydrates. To compare sensitivity of IPAD and MS detection glucose, fructose, and sucrose were used as analytes. A calibration with external standards from 2.5 to 1000 pmole was performed showing a linear range over three orders of magnitude. Minimum detection limits (MDL) with IPAD were determined at 5 pmole levels for glucose to be 0.12 pmole, fructose 0.22 pmole and sucrose 0.11 pmole. With MS detection in the selected ion mode (SIM) the lithium adducts of the carbohydrates were detected obtaining MDL's for glucose of 1.49 pmole, fructose 1.19 pmole, and sucrose 0.36 pmole showing that under these conditions IPAD is 3-10 times more sensitive for those carbohydrates. The applicability of the method was demonstrated analysing carbohydrates in real world samples such as chicory inulin where polyfructans up to a molecular mass of 7000 g/mol were detected as quadrupoly charged lithium adducts. Furthermore mono-, di-, tri-, and oligosaccharides were detected in chicory coffee, honey and beer samples. PMID:16106855

  6. Anion exchangers with branched functional ion exchange layers of different hydrophilicity for ion chromatography.

    PubMed

    Shchukina, O I; Zatirakha, A V; Smolenkov, A D; Nesterenko, P N; Shpigun, O A

    2015-08-21

    Novel polystyrene-divinylbenzene (PS-DVB) based anion exchangers differing from each other in the structure of the branched functional ion exchange layer are prepared to investigate the role of linker and functional site on ion exchange selectivity. The proposed method of synthesis includes the obtaining of aminated PS-DVB particles by means of their acylation with following reductive amination with methylamine. Further modification of the obtained secondary aminogroups is provided by the alkylation with either 1,4-butanediol diglycidyl ether (1,4-BDDGE) or resorcinol diglycidyl ether (RDGE), which form the linkers of different hydrophobicity, and amination of terminal epoxide rings with trimethylamine (TMA), dimethylethanolamine (DMEA), methyldiethanolamine (MDEA) or triethanolamine (TEA). The variation of the structure and hydrophobicity of the linker and terminal quaternary ammonium sites in the functional layer allows the alteration of selectivity and separation efficiency of the obtained adsorbents. The ion exchange selectivity and separation efficiency of the anion exchangers are evaluated using the model mixtures of anions (F(-), HCOO(-), Cl(-), NO2(-), Br(-), NO3(-), HPO4(2-) and SO4(2-)) in potassium hydroxide eluents. The adsorbents show the decrease of selectivity with increasing the hydrophilicity of the terminal functional site. The anion exchangers having more flexible and hydrophilic 1,4-BDDGE linker provide smaller separation factors for most of the analytes as compared with RDGE-containing adsorbents with the same terminal ion exchange sites, but are characterized with higher column efficiencies and better peak symmetry for polarizable anions. In case of 1,4-BDDGE-modified anion exchangers of the particle size of 3.3μm functionalized with DMEA and MDEA the calculated values of column efficiencies for polarizable NO3(-) and Br(-) are up to 49,000 and 53,000N/m, respectively, which is almost twice higher than the values obtained for the RDGE

  7. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... area of the eye. (d) Labeling requirements. The label of the color additive and of any mixtures... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1326 Chromium hydroxide green. (a) Identity. (1) The color additive chromium hydroxide green is principally hydrated chromic sesquioxide...

  8. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... area of the eye. (d) Labeling requirements. The label of the color additive and of any mixtures... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1326 Chromium hydroxide green. (a) Identity. (1) The color additive chromium hydroxide green is principally hydrated chromic sesquioxide...

  9. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... area of the eye. (d) Labeling requirements. The label of the color additive and of any mixtures... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1326 Chromium hydroxide green. (a) Identity. (1) The color additive chromium hydroxide green is principally hydrated chromic sesquioxide...

  10. 21 CFR 872.3250 - Calcium hydroxide cavity liner.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Calcium hydroxide cavity liner. 872.3250 Section 872.3250 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3250 Calcium hydroxide cavity liner....

  11. 21 CFR 872.3250 - Calcium hydroxide cavity liner.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Calcium hydroxide cavity liner. 872.3250 Section 872.3250 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3250 Calcium hydroxide cavity liner....

  12. 40 CFR 721.4467 - Quaternary ammonium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Quaternary ammonium hydroxide. 721... Substances § 721.4467 Quaternary ammonium hydroxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a quaternary ammonium...

  13. 40 CFR 721.4467 - Quaternary ammonium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Quaternary ammonium hydroxide. 721... Substances § 721.4467 Quaternary ammonium hydroxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a quaternary ammonium...

  14. Ion chromatographic determination of hydroxide ion on monolithic reversed-phase silica gel columns coated with nonionic and cationic surfactants.

    PubMed

    Xu, Qun; Mori, Masanobu; Tanaka, Kazuhiko; Ikedo, Mikaru; Hu, Wenzhi; Haddad, Paul R

    2004-07-01

    The determination of hydroxide by ion chromatography (IC) is demonstrated using a monolithic octadecylsilyl (ODS)-silica gel column coated first with a nonionic surfactant (polyoxyethylene (POE)) and then with a cationic surfactant (cetyltrimethylammonium bromide (CTAB)). This stationary phase, when used in conjunction with a 10 mmol/l sodium sulfate eluent at pH 8.2, was found to be suitable for the rapid and efficient separation of hydroxide from some other anions, based on a conventional ion-exchange mechanism. The peak directions and detection responses for these ions were in agreement with their known limiting equivalent ionic conductance values. Under these conditions, a linear calibration plot was obtained for hydroxide ion over the range 16 micromol/l to 15 mmol/l, and the detection limit determined at a signal-to-noise ratio of 3 was 6.4 micromol/l. The double-coated stationary phase described above was shown to be superior to a single coating of cetyltrimethylammonium bromide alone, in terms of separation efficiency and stability of the stationary phase. A range of samples comprising solutions of some strong and weak bases was analyzed by the proposed method and the results obtained were in good agreement with those obtained by conventional potentiometric pH measurement.

  15. Interfacial and near interfacial crack growth phenomena in metal bonded alumina

    SciTech Connect

    Kruzic, Jamie Joseph

    2002-03-01

    Metal/ceramic interfaces can be found in many engineering applications including microelectronic packaging, multi-layered films, coatings, joints, and composite materials. In order to design reliable engineering systems that contain metal/ceramic interfaces, a comprehensive understanding of interfacial and near interfacial failure mechanisms is necessary.

  16. Intercalation studies of zinc hydroxide chloride: Ammonia and amino acids

    SciTech Connect

    Arizaga, Gregorio Guadalupe Carbajal

    2012-01-15

    Zinc hydroxide chloride (ZHC) is a layered hydroxide salt with formula Zn{sub 5}(OH){sub 8}Cl{sub 2}{center_dot}2H{sub 2}O. It was tested as intercalation matrix for the first time and results were compared with intercalation products of the well-known zinc hydroxide nitrate and a Zn/Al layered double hydroxide. Ammonia was intercalated into ZHC, while no significant intercalation occurred in ZHN. Aspartic acid intercalation was only achieved by co-precipitation at pH=10 with ZHC and pH=8 with zinc hydroxide nitrate. Higher pH resistance in ZHC favored total deprotonation of both carboxylic groups of the Asp molecule. ZHC conferred more thermal protection against Asp combustion presenting exothermic peaks even at 452 Degree-Sign C while the exothermic event in ZHN was 366 Degree-Sign C and in the LDH at 276 Degree-Sign C. - Graphical abstract: The zinc hydroxide chloride (ZHC) with formula Zn{sub 5}(OH){sub 8}Cl{sub 2}{center_dot}2H{sub 2}O was tested as intercalation matrix. In comparison with the well-known zinc hydroxide nitrate (ZHN) and layered double hydroxides (LDH), ZHC was the best matrix for thermal protection of Asp combustion, presenting exothermic peaks even at 452 Degree-Sign C, while the highest exothermic event in ZHN was at 366 Degree-Sign C, and in the LDH it was at 276 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Zinc hydroxide chloride (ZHC) was tested as intercalation matrix for the first time. Black-Right-Pointing-Pointer ZHC has higher chemical and thermal stability than zinc hydroxide nitrate and LDH. Black-Right-Pointing-Pointer NH{sub 3} molecules can be intercalated into ZHC. Black-Right-Pointing-Pointer The amino group of amino acids limits the intercalation by ion-exchange.

  17. Immobilization of anionic iron(III) porphyrins onto in situ obtained zinc oxide.

    PubMed

    Machado, Guilherme S; Wypych, Fernando; Nakagaki, Shirley

    2012-07-01

    A family of anionic iron(III) porphyrins (FePor) was immobilized onto zinc oxide (ZnO) obtained by the in situ hydrothermal decomposition of zinc hydroxide nitrate, a layered hydroxide salt. The immobilization probably occurred via the interaction between the anionic charges on the porphyrins and the positively charged surface of the ZnO, in slightly acidic to neutral pH. The resulting solids were characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRDP), Fourier transform infrared spectroscopy (FTIR), electron paramagnetic resonance (EPR), and ultraviolet-visible spectroscopy (UV-Vis) (solid samples), which confirmed the formation of ZnO and the immobilization of the FePor. The prepared materials were employed as catalysts for the heterogeneous catalytic oxidation of cyclooctene, cyclohexane, and n-heptane, using iodosylbenzene as the oxygen donor. Good catalytic results were achieved for all the substrates, and selectivity for the alcohol was verified during the oxidation of alkanes. The reuse capacity of the solid catalyst was also investigated.

  18. [Determination of sulfide in gourmet powder by anion exchange chromatography with pulsed amperometric detection].

    PubMed

    Li, Renyong; Liang, Lina; Li, Jing

    2010-12-01

    A chromatographic method was developed for the determination of sulfide in gourmet powder. The samples were dissolved in 2 g/L sodium hydroxide solution directly, and filtrated with a 0.22 microm nylon membrane. The sulfide and other anions such as high concentration of glutamate were separated well in 6 min by an IonPac AS7 Anion Exchange column (250 mm x4 mm). A mixed solution of 100 mmol/L sodium hydroxide, 500 mmol/L sodium acetate and 0.5% ethylenediamine was used isocratically as the mobile phase. The detection limit of the sulfide was 0.3 microg/L at 25 microL injection (S/N = 3). Moreover, the method had a wide linear range (0.001-1 mg/L) and satisfactory recovery (94.2%-99.0%). The method was applied in the determinations of the sulfide in 99% monosodium glutamate, special delicious monosodium glutamate and salted monosodium glutamate samples. The method is simple, fast and good in separation performance, and has high selectivity and sensitivity.

  19. Effects of Anions on Local Structure of Al and Si in Aluminosilicates.

    PubMed

    Miyazaki; Yokoyama

    1999-06-15

    Three kinds of amorphous aluminosilicates were synthesized by coprecipitation of silicic acid with aluminum hydroxide in the presence of different inorganic ions: sulfate, chloride, and nitrate. Although the bulk composition of the aluminosilicates obtained was not affected by anion species, their DTA spectra were significantly different, suggesting that their structures also differ. The local structure of Al and Si in the aluminosilicates was studied in detail by 27Al and 29Si MAS NMR. From the 27Al MAS NMR spectra and comparison between 29Si HD- and CP-MAS NMR spectra, it was concluded that the aluminosilicate obtained in the presence of sulfate ions has only a montmorillonite-like structure, whereas in the cases of chloride and nitrate, the solids are composed of three phases: aluminum hydroxide, silica, and the montmorillonite-like aluminosilicate. The difference in the local structure of Al and Si in the aluminosilicates was explained by the difference in interaction between the anions and aluminum ions. Copyright 1999 Academic Press.

  20. Effects of anions on local structure of Al and Si in aluminosilicates

    SciTech Connect

    Miyazaki, Akane; Yokoyama, Takushi

    1999-06-15

    Three kinds of amorphous aluminosilicates were synthesized by coprecipitation of silicic acid with aluminum hydroxide in the presence of different inorganic ions: sulfate, chloride, and nitrate. Although the bulk composition of the aluminosilicates obtained was not affected by anion species, their DTA spectra were significantly different, suggesting that their structures also differ. The local structure of Al and Si in the aluminosilicates was studied in detail by {sup 27}Al and {sup 29}Si MAS NMR. From the {sup 27}Al MAS NMR spectra and comparison between {sup 29}Si HD- and CP-MAS NMR spectra, it was concluded that the aluminosilicate obtained in the presence of sulfate ions has only a montmorillonite-like structure, whereas in the cases of chloride and nitrate, the solids are composed of three phases: aluminum hydroxide, silica, and the montmorillonite-like aluminosilicate. The difference in the local structure of Al and Si in the aluminosilicates was explained by the difference in interaction between the anions and aluminum ions.

  1. Influence of alkyl chain length and anion species on ionic liquid structure at the graphite interface as a function of applied potential.

    PubMed

    Li, Hua; Wood, Ross J; Endres, Frank; Atkin, Rob

    2014-07-16

    Atomic force microscopy (AFM) force measurements elucidate the effect of cation alkyl chain length and the anion species on ionic liquid (IL) interfacial structure at highly ordered pyrolytic graphite (HOPG) surfaces as a function of potential. Three ILs are examined: 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM] FAP), 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM] FAP), and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] TFSA). The step-wise force-distance profiles indicate the ILs adopt a multilayered morphology near the surface. When the surface is biased positively or negatively versus Pt quasireference electrode, both the number of steps, and the force required to rupture each step increase, indicating stronger interfacial structure. At all potentials, push-through forces for [HMIM] FAP are the highest, because the long alkyl chain results in strong cohesive interactions between cations, leading to well-formed layers that resist the AFM tip. The most layers are observed for [EMIM] FAP, because the C2 chains are relatively rigid and the dimensions of the cation and anion are similar, facilitating neat packing. [EMIM] TFSA has the smallest push-through forces and fewest layers, and thus the weakest interfacial structure. Surface-tip attractive forces are measured for all ILs. At the same potential, the attractions are the strongest for [EMIM] TFSA and the weakest for [HMIM] FAP because the interfacial layers are better formed for the longer alkyl chain cation. This means interfacial forces are stronger, which masks the weak attractive forces.

  2. Interfacial area and interfacial transfer in two-phase systems. DOE final report

    SciTech Connect

    Ishii, Mamoru; Hibiki, T.; Revankar, S.T.; Kim, S.; Le Corre, J.M.

    2002-07-01

    In the two-fluid model, the field equations are expressed by the six conservation equations consisting of mass, momentum and energy equations for each phase. The existence of the interfacial transfer terms is one of the most important characteristics of the two-fluid model formulation. The interfacial transfer terms are strongly related to the interfacial area concentration and to the local transfer mechanisms such as the degree of turbulence near interfaces. This study focuses on the development of a closure relation for the interfacial area concentration. A brief summary of several problems of the current closure relation for the interfacial area concentration and a new concept to overcome the problem are given.

  3. Cu-Ce-O mixed oxides from Ce-containing layered double hydroxide precursors: Controllable preparation and catalytic performance

    SciTech Connect

    Chang Zheng; Zhao Na; Liu Junfeng; Li Feng; Evans, David G.; Duan Xue; Forano, Claude; Roy, Marie de

    2011-12-15

    Cu/Zn/Al layered double hydroxide (LDH) precursors have been synthesized using an anion exchange method with anionic Ce complexes containing the dipicolinate (pyridine-2,6-dicarboxylate) ligand. Cu-Ce-O mixed oxides were obtained by calcination of the Ce-containing LDHs. The materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, and low temperature N{sub 2} adsorption/desorption measurements. The results reveal that the inclusion of Ce has a significant effect on the specific surface area, pore structure, and chemical state of Cu in the resulting Cu-Ce-O mixed metal oxides. The resulting changes in composition and structure, particularly the interactions between Cu and Ce centers, significantly enhance the activity of the Ce-containing materials as catalysts for the oxidation of phenol by hydrogen peroxide. - Graphical Abstract: Cu-Ce-O mixed oxides calcined from [Ce(dipic){sub 3}]{sup 3-}- intercalated Cu/Zn/Al layered double hydroxides were synthesized and displayed good catalytic performances in phenol oxidation due to the Cu-Ce interactions. Highlights: Black-Right-Pointing-Pointer [Ce(dipic){sub 3}]{sup 3-}-intercalated Cu/Zn/Al layered double hydroxides were synthesized. Black-Right-Pointing-Pointer Cu-Ce-O mixed oxides derivated from the LDHs were characterized as catalysts. Black-Right-Pointing-Pointer Presence of Ce influenced physicochemical property and catalytic performance. Black-Right-Pointing-Pointer Cu-Ce interaction was largely responsible for enhanced catalytic ability.

  4. High pseudocapacitive cobalt carbonate hydroxide films derived from CoAl layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Lu, Zhiyi; Zhu, Wei; Lei, Xiaodong; Williams, Gareth R.; O'Hare, Dermot; Chang, Zheng; Sun, Xiaoming; Duan, Xue

    2012-05-01

    A thin nanosheet of mesoporous cobalt carbonate hydroxide (MPCCH) has been fabricated from a CoAl-LDH nanosheet following removal of the Al cations by alkali etching. The basic etched electrode exhibits enhanced specific capacitance (1075 F g-1 at 5 mA cm-2) and higher rate capability and cycling stability (92% maintained after 2000 cycles).A thin nanosheet of mesoporous cobalt carbonate hydroxide (MPCCH) has been fabricated from a CoAl-LDH nanosheet following removal of the Al cations by alkali etching. The basic etched electrode exhibits enhanced specific capacitance (1075 F g-1 at 5 mA cm-2) and higher rate capability and cycling stability (92% maintained after 2000 cycles). Electronic supplementary information (ESI) available: Detailed experimental procedure, specific capacitance calculation, EDS and FTIR results, electrochemical results of CoAl-LDH and SEM image. See DOI: 10.1039/c2nr30617d

  5. Short-time hydrothermal synthesis and delamination of ion exchangeable Mg/Ga layered double hydroxides

    SciTech Connect

    Unal, Ugur

    2007-09-15

    The hydrothermal synthesis of magnesium-gallium layered double hydroxides (Mg/Ga LDHs) was studied under static and agitated conditions. Not only well-crystallized and large-sized Mg/Ga LDHs having hexagonal morphology were obtained but also the reaction time was comparatively decreased from 24 to 2 h by means of agitation during hydrothermal synthesis. In static conditions, mainly GaOOH and magnesite phases were formed. The elemental analysis results show that the final Mg/Ga ratio is significantly different from the initial ratio. The reason was attributed to the difference in the hydrolytic behavior of Mg{sup 2+} and Ga{sup 3+}. Furthermore, the anion exchange studies with glycine, dodecyl sulfate, ferrocyanide and ferricyanide were performed to investigate the intercalation behavior of the anions into Mg/Ga LDHs. In addition, delamination of Mg/Ga LDHs was performed in formamide for the glycine exchanged forms. Large size of nanosheets thus obtained can be utilized in the fabrication of functional thin films. - Graphical abstract: Hydrothermal synthesis under agitation resulted in highly crystalline Mg/Ga LDHs slabs in a short time. The LDHs slabs were delaminated into two-dimensional nanosize sheets.

  6. Fire and thermal properties of layered double hydroxides and polyurea nanocomposites

    NASA Astrophysics Data System (ADS)

    Nyambo, Calistor

    Layered double hydroxide (LDH) intercalated with linear alkyl carboxylates (CH3(CH2)n COO-, n = 8, 10, 12, 14, 16, 20), borate and benzyl anions were prepared. The effect on fire and thermal properties of the mode of preparation for LDHs (i.e. ion exchange, coprecipitation and rehydration of the calcined LDH methods) has been studied. After characterization, the LDHs were used to prepare nanocomposites with a range of polar and non-polar polymers. Characterization of the LDHs and the nanocomposites was performed using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetry analysis (TGA), transmission electron microscopy (TEM) and cone calorimetry. FTIR and XRD analyses confirmed the presence of the charge balancing anions in the galleries of the LDHs. Improvements in fire and thermal properties of the nanocomposites were observed. The cone calorimeter revealed that the addition of LDHs reduces the peak heat release rate significantly. LDHs were combined with commercial fire retardants. Synergistic effects were observed in both TGA and cone calorimetry for formulations containing both LDH and ammonium polyphosphate (APP). Physical and chemical interactions between LDH and APP are responsible for the observed synergy in thermal stability and fire performance.

  7. Carboxylate-intercalated layered double hydroxides aged under microwave-hydrothermal treatment

    NASA Astrophysics Data System (ADS)

    Benito, P.; Labajos, F. M.; Mafra, L.; Rocha, J.; Rives, V.

    2009-01-01

    Carboxylate-intercalated (terephthalate, TA and oxalate, ox) layered double hydroxides (LDHs) are aged under a microwave-hydrothermal treatment. The influence of the nature of the interlayer anion during the ageing process is studied. Characterization results show that the microwave-hydrothermal method can be extended to synthesize LDHs with anions different than carbonate, like TA. LDH-TA compounds are stable under microwave irradiation for increasing periods of time and the solids show an improved order both in the layers and in the interlayer region as evidenced by powder X-ray diffraction (PXRD), 27Al MAS NMR and FT-IR spectroscopy. Furthermore, cleaning of the surface through removal of some organic species adsorbed on the surface of the particles also occurs during the microwave-hydrothermal treatment. Conversely, although the expected increase in crystallinity is observed in LDH-ox samples, the side-reaction between Al 3+ and ox is also enhanced under microwave irradiation, and a partial destruction of the structure takes place with an increase in the M 2+/M 3+ ratio and consequent modification of the cell parameters.

  8. Recyclable Mg-Al layered double hydroxides for fluoride removal: Kinetic and equilibrium studies.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2015-12-30

    Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg-Al LDH) and Cl(-) (Cl · Mg-Al LDH) were found to adsorb fluoride from aqueous solutions. Fluoride is removed by anion exchange in solution with NO3(-) and Cl(-) intercalated in the LDH interlayer. In both cases, the residual F concentration is lower than the effluent standards for F in Japan (8 mg/L). The rate-determining step in the removal of F using NO3 · Mg-Al and Cl · Mg-Al LDH is chemical adsorption involving F(-) anion exchange with intercalated NO3(-) and Cl(-) ions. The removal of F is described by pseudo-second-order reaction kinetics, with Langmuir-type adsorption. The values obtained for the maximum adsorption and the equilibrium adsorption constant are respectively 3.3 mmol g(-1) and 2.8 with NO3 · Mg-Al LDH, and 3.2 mmol g(-1) and 1.5 with Cl · Mg-Al LDH. The F in the F · Mg-Al LDH produced in these reactions was found to exchange with NO3(-) and Cl(-) ions in solution. The regenerated NO3 · Mg-Al and Cl · Mg-Al LDHs thus obtained can be used once more to capture aqueous F. This suggests that NO3 · Mg-Al and Cl · Mg-Al LDHs can be recycled and used repeatedly for F removal.

  9. Complex Microfiltration Behavior of Metal Hydroxide Slurries

    SciTech Connect

    Shimskey, Rick W.; Schonewill, Philip P.; Daniel, Richard C.; Peterson, Reid A.

    2011-02-28

    Crossflow filtration is to be a key process in the treatment and disposal of approximately 60,000 metric tons of high-level waste stored at the Hanford Site in Richland, Washington. Pacific Northwest National Laboratory is assessing filter performance against waste simulant materials that mimic the chemical and physical properties of Hanford tank waste. Prior simulant studies indicate that waste filtration performance may be limited by pore and cake fouling. To limit the shutdown of waste treatment operations, the pre-treatment facility plans to recover filter flux loses from cake formation and filter fouling by frequently backpulsing the filter elements. The objective of the current research is to develop an understanding of the roles of cake and pore fouling and potential flux recovery through backpulsing of the filters for Hanford waste filtration operations. Metal hydroxide wastes were tested to examine the role of particle-filter interaction on filter performance.

  10. Pickering emulsion templated interfacial atom transfer radical polymerization for microencapsulation.

    PubMed

    Li, Jian; Hitchcock, Adam P; Stöver, Harald D H

    2010-12-01

    This Article describes a new microencapsulation method based on a Pickering emulsion templated interfacial atom transfer radical polymerization (PETI-ATRP). Cationic LUDOX CL nanoparticles were coated electrostatically with an anionic polymeric ATRP initiator, poly(sodium styrene sulfonate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate) (PSB), prepared by radical copolymerization of sodium styrene sulfonate and 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM). The resulting PSB-modified CL particles were surface active and could be used to stabilize oil-in-water Pickering emulsions. ATRP of water-soluble cross-linking monomers, confined to the oil-water interface by the surface-bound PSB, then led to nanoparticle/polymer composite shells. This method allowed encapsulation of core solvents (xylene, hexadecane, perfluoroheptane) with different solubility parameters. The microcapsule (MC) wall chemistry could accommodate different monomers, demonstrating the versatility of this method. Double-walled MCs were formed by sequentially carrying out PETI-ATRP and in situ polymerization of encapsulated monomers. The double-walled structure was verified by both transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  11. Asymmetric Transport Mechanisms of Hydronium and Hydroxide Ions in Amorphous Solid Water: Hydroxide Goes Brownian while Hydronium Hops.

    PubMed

    Lee, Du Hyeong; Choi, Cheol Ho; Choi, Tae Hoon; Sung, Bong June; Kang, Heon

    2014-08-01

    The diffusion of hydronium (H3O(+)) and hydroxide (OH(-)) ions is one of the most intriguing topics in aqueous chemistry. It is considered that these ions in aqueous solutions move via sequential proton transfer events, known as the Grotthuss mechanisms. Here, we present an experimental study of the diffusion and H/D exchange of hydronium and hydroxide ions in amorphous solid water (ASW) at 140-180 K by using low-energy sputtering (LES) and temperature-programmed desorption (TPD) measurements. The study shows that the two species transport in ASW via fundamentally different molecular mechanisms. Whereas hydronium ions migrate via efficient proton transfer, hydroxide ions move via Brownian molecular diffusion without proton transfer. The molecular hydroxide diffusion in ASW is in stark contrast to the current view of the hydroxide diffusion mechanism in aqueous solution, which involves proton transfer.

  12. Contributions of residues of pancreatic phospholipase A2 to interfacial binding, catalysis, and activation.

    PubMed

    Yu, B Z; Rogers, J; Tsai, M D; Pidgeon, C; Jain, M K

    1999-04-13

    Primary rate and equilibrium parameters for 60 site-directed mutants of bovine pancreatic phospholipase A2 (PLA2) are analyzed so incremental contributions of the substitution of specific residues can be evaluated. The magnitude of the change is evaluated so a functional role in the context of the N- and C-domains of PLA2 can be assigned, and their relationship to the catalytic residues and to the i-face that makes contact with the interface. The effect of substitutions and interfacial charge is characterized by the equilibrium dissociation constant for dissociation of the bound enzyme from the interface (Kd), the dissociation constant for dissociation of a substrate mimic from the active site of the bound enzyme (KL), and the interfacial Michaelis constants, KM and kcat. Activity is lost (>99.9%) on the substitution of H48 and D49, the catalytic residues. A more than 95% decrease in kcat is seen with the substitution of F5, I9, D99, A102, or F106, which form the substrate binding pocket. Certain residues, which are not part of the catalytic site or the substrate binding pocket, also modulate kcat. Interfacial anionic charge lowers Kd, and induces kcat activation through K56, K53, K119, or K120. Significant changes in KL are seen by the substitution of N6, I9, F22, Y52, K53, N71, Y73, A102, or A103. Changes in KM [=(k2+k-1)/k1] are attributed to kcat (=k2) and KL (=k-1/k1). Some substitutions change more than one parameter, implying an allosteric effect of the binding to the interface on KS, and the effect of the interfacial anionic charge on kcat. Interpreted in the context of the overall structure, results provide insights into the role of segments and domains in the microscopic events of catalytic turnover and processivity, and their allosteric regulation. We suggest that the interfacial recognition region (i-face) of PLA2, due to the plasticity of certain segments and domains, exercises an allosteric control on the substrate binding and chemical step.

  13. Efficient uranium capture by polysulfide/layered double hydroxide composites.

    PubMed

    Ma, Shulan; Huang, Lu; Ma, Lijiao; Shim, Yurina; Islam, Saiful M; Wang, Pengli; Zhao, Li-Dong; Wang, Shichao; Sun, Genban; Yang, Xiaojing; Kanatzidis, Mercouri G

    2015-03-18

    There is a need to develop highly selective and efficient materials for capturing uranium (normally as UO2(2+)) from nuclear waste and from seawater. We demonstrate the promising adsorption performance of S(x)-LDH composites (LDH is Mg/Al layered double hydroxide, [S(x)](2-) is polysulfide with x = 2, 4) for uranyl ions from a variety of aqueous solutions including seawater. We report high removal capacities (q(m) = 330 mg/g), large K(d)(U) values (10(4)-10(6) mL/g at 1-300 ppm U concentration), and high % removals (>95% at 1-100 ppm, or ∼80% for ppb level seawater) for UO2(2+) species. The S(x)-LDHs are exceptionally efficient for selectively and rapidly capturing UO2(2+) both at high (ppm) and trace (ppb) quantities from the U-containing water including seawater. The maximum adsorption coeffcient value K(d)(U) of 3.4 × 10(6) mL/g (using a V/m ratio of 1000 mL/g) observed is among the highest reported for U adsorbents. In the presence of very high concentrations of competitive ions such as Ca(2+)/Na(+), S(x)-LDH exhibits superior selectivity for UO2(2+), over previously reported sorbents. Under low U concentrations, (S4)(2-) coordinates to UO2(2+) forming anionic complexes retaining in the LDH gallery. At high U concentrations, (S4)(2-) binds to UO2(2+) to generate neutral UO2S4 salts outside the gallery, with NO3(-) entering the interlayer to form NO3-LDH. In the presence of high Cl(-) concentration, Cl(-) preferentially replaces [S4](2-) and intercalates into LDH. Detailed comparison of U removal efficiency of S(x)-LDH with various known sorbents is reported. The excellent uranium adsorption ability along with the environmentally safe, low-cost constituents points to the high potential of S(x)-LDH materials for selective uranium capture.

  14. Carboxylate-intercalated layered double hydroxides aged under microwave-hydrothermal treatment

    SciTech Connect

    Benito, P.; Labajos, F.M.; Mafra, L.; Rocha, J.; Rives, V.

    2009-01-15

    Carboxylate-intercalated (terephthalate, TA and oxalate, ox) layered double hydroxides (LDHs) are aged under a microwave-hydrothermal treatment. The influence of the nature of the interlayer anion during the ageing process is studied. Characterization results show that the microwave-hydrothermal method can be extended to synthesize LDHs with anions different than carbonate, like TA. LDH-TA compounds are stable under microwave irradiation for increasing periods of time and the solids show an improved order both in the layers and in the interlayer region as evidenced by powder X-ray diffraction (PXRD), {sup 27}Al MAS NMR and FT-IR spectroscopy. Furthermore, cleaning of the surface through removal of some organic species adsorbed on the surface of the particles also occurs during the microwave-hydrothermal treatment. Conversely, although the expected increase in crystallinity is observed in LDH-ox samples, the side-reaction between Al{sup 3+} and ox is also enhanced under microwave irradiation, and a partial destruction of the structure takes place with an increase in the M{sup 2+}/M{sup 3+} ratio and consequent modification of the cell parameters. - Graphical Abstract: The influence of the nature of the interlayer anion during the ageing process of carboxylate-intercalated (TA and ox) hydrotalcite-like compounds (HTlcs) is studied. Well crystallized for TA-containing compounds were obtained. However, the non-desired side-reaction of ox with the aluminum of the layers is enhanced by the microwaves and a partial destruction of the structure takes place.

  15. Ternary Complexation on Bacterial Surfaces: Implications for Subsurface Anion Transport

    NASA Astrophysics Data System (ADS)

    Maclean, L. C.; Higginbottom, C. M.; Fowle, D. A.

    2002-12-01

    (VI) and I- in the presence of background electrolyte and aqueous Al (III), Cd(II), Ca(II) or cells coated with Al (oxy)hydroxide phases. We use a unique blend of XRD, electrophoretic mobility, SEM, and aqueous geochemistry measurements to quantify the mechanisms of Cr(VI) and I- removal from solution. Our results indicate the removal of both anions is highly dependent on solution pH with significant removal at low pH and diminishing removal at higher pH values, without the presence of cations or precipitates. However, in the presence of aqueous Cd(II) and Ca(II) which adsorbs strongly from pH 3.5-8, the removal of Cr(VI) and I- increases appreciably. Furthermore the loading of the cell surface with small amorphous mineral phases increases adsorption. Aging of the mineral-bacteria composites appears to decrease removal efficiency due to coarsening of the mineral phases and a decrease in charge density. Considering that many geologic environments include both cationic and anionic metal contaminants, our results suggest that mass transport of Cr(VI), I-, and other anions may be affected by ternary complexation or other cation mediated surface reactions in bacteria-bearing systems.

  16. Different Arsenate and Phosphate Incorporation Effects on the Nucleation and Growth of Iron(III) (Hydr)oxides on Quartz

    SciTech Connect

    Neil, Chelsea W.; Lee, Byeongdu; Jun, Young-Shin

    2014-10-21

    Iron(III) (hydr)oxides play an important role in the geochemical cycling of contaminants in natural and engineered aquatic systems. The ability of iron(III) (hydr)oxides to immobilize contaminants can be related to whether the precipitates form heterogeneously (e.g., at mineral surfaces) or homogeneously in solution. Utilizing grazing incidence small-angle X-ray scattering (GISAXS), we studied heterogeneous iron(III) (hydr)oxide nucleation and growth on quartz substrates for systems containing arsenate and phosphate anions. For the iron(III) only system, the radius of gyration ( R g ) of heterogeneously formed precipitates grew from 1.5 to 2.5 ( ± 1.0) nm within 1 h. For the system containing 10-5 M arsenate, R g grew from 3.6 to 6.1 ( ± 0.5) nm, and for the system containing 10-5 M phosphate, R g grew from 2.0 to 4.0 ( ± 0.2) nm. While the systems containing these oxyanions had more growth, the system containing only iron(III) had the most nucleation events on substrates. Ex situ analyses of homogeneously and heterogeneously formed precipitates indicated that precipitates in the arsenate system had the highest water content and that oxyanions may bridge iron(III) hydroxide polymeric embryos to form a structure similar to ferric arsenate or ferric phosphate. These new fi ndings are important because di ff erences in nucleation and growth rates and particle sizes will impact the number of available reactive sites and the reactivity of newly formed particles toward aqueous contaminants.

  17. Different arsenate and phosphate incorporation effects on the nucleation and growth of iron(III) (Hydr)oxides on quartz.

    PubMed

    Neil, Chelsea W; Lee, Byeongdu; Jun, Young-Shin

    2014-10-21

    Iron(III) (hydr)oxides play an important role in the geochemical cycling of contaminants in natural and engineered aquatic systems. The ability of iron(III) (hydr)oxides to immobilize contaminants can be related to whether the precipitates form heterogeneously (e.g., at mineral surfaces) or homogeneously in solution. Utilizing grazing incidence small-angle X-ray scattering (GISAXS), we studied heterogeneous iron(III) (hydr)oxide nucleation and growth on quartz substrates for systems containing arsenate and phosphate anions. For the iron(III) only system, the radius of gyration (Rg) of heterogeneously formed precipitates grew from 1.5 to 2.5 (± 1.0) nm within 1 h. For the system containing 10(-5) M arsenate, Rg grew from 3.6 to 6.1 (± 0.5) nm, and for the system containing 10(-5) M phosphate, Rg grew from 2.0 to 4.0 (± 0.2) nm. While the systems containing these oxyanions had more growth, the system containing only iron(III) had the most nucleation events on substrates. Ex situ analyses of homogeneously and heterogeneously formed precipitates indicated that precipitates in the arsenate system had the highest water content and that oxyanions may bridge iron(III) hydroxide polymeric embryos to form a structure similar to ferric arsenate or ferric phosphate. These new findings are important because differences in nucleation and growth rates and particle sizes will impact the number of available reactive sites and the reactivity of newly formed particles toward aqueous contaminants.

  18. Different arsenate and phosphate incorporation effects on the nucleation and growth of iron(III) (Hydr)oxides on quartz.

    PubMed

    Neil, Chelsea W; Lee, Byeongdu; Jun, Young-Shin

    2014-10-21

    Iron(III) (hydr)oxides play an important role in the geochemical cycling of contaminants in natural and engineered aquatic systems. The ability of iron(III) (hydr)oxides to immobilize contaminants can be related to whether the precipitates form heterogeneously (e.g., at mineral surfaces) or homogeneously in solution. Utilizing grazing incidence small-angle X-ray scattering (GISAXS), we studied heterogeneous iron(III) (hydr)oxide nucleation and growth on quartz substrates for systems containing arsenate and phosphate anions. For the iron(III) only system, the radius of gyration (Rg) of heterogeneously formed precipitates grew from 1.5 to 2.5 (± 1.0) nm within 1 h. For the system containing 10(-5) M arsenate, Rg grew from 3.6 to 6.1 (± 0.5) nm, and for the system containing 10(-5) M phosphate, Rg grew from 2.0 to 4.0 (± 0.2) nm. While the systems containing these oxyanions had more growth, the system containing only iron(III) had the most nucleation events on substrates. Ex situ analyses of homogeneously and heterogeneously formed precipitates indicated that precipitates in the arsenate system had the highest water content and that oxyanions may bridge iron(III) hydroxide polymeric embryos to form a structure similar to ferric arsenate or ferric phosphate. These new findings are important because differences in nucleation and growth rates and particle sizes will impact the number of available reactive sites and the reactivity of newly formed particles toward aqueous contaminants. PMID:25232994

  19. Adsorption affinity of anions on metal oxyhydroxides

    NASA Astrophysics Data System (ADS)

    Pechenyuk, S. I.; Semushina, Yu. P.; Kuz'mich, L. F.

    2013-03-01

    The dependences of anion (phosphate, carbonate, sulfate, chromate, oxalate, tartrate, and citrate) adsorption affinity anions from geometric characteristics, acid-base properties, and complex forming ability are generalized. It is shown that adsorption depends on the nature of both the anions and the ionic medium and adsorbent. It is established that anions are generally grouped into the following series of adsorption affinity reduction: PO{4/3-}, CO{3/2-} > C2O{4/2-}, C(OH)(CH2)2(COO){3/3-}, (CHOH)2(COO){2/2-} > CrO{4/2-} ≫ SO{4/2-}.

  20. Microfluidic ultralow interfacial tensiometry with magnetic particles.

    PubMed

    Tsai, Scott S H; Wexler, Jason S; Wan, Jiandi; Stone, Howard A

    2013-01-01

    We describe a technique that measures ultralow interfacial tensions using paramagnetic spheres in a co-flow microfluidic device designed with a magnetic section. Our method involves tuning the distance between the co-flowing interface and the magnet's center, and observing the behavior of the spheres as they approach the liquid-liquid interface-the particles either pass through or are trapped by the interface. Using threshold values of the magnet-to-interface distance, we make estimates of the two-fluid interfacial tension. We demonstrate the effectiveness of this technique for measuring very low interfacial tensions, O(10(-6)-10(-5)) N m(-1), by testing solutions of different surfactant concentrations, and we show that our results are comparable with measurements made using a spinning drop tensiometer. PMID:23154819

  1. A swarm of Stokeslets with interfacial tension

    NASA Astrophysics Data System (ADS)

    Nitsche, Ludwig C.; Schaflinger, Uwe

    2001-06-01

    A formal analogy between sedimenting drops in Stokes flow and a swarm of Stokeslets [Machu et al., J. Fluid Mech. (in press)] is extended to include interfacial tension. Using a cohesive potential, mean curvature is extended as a meaningful quantity off the interface, allowing the boundary-integral formulation to be rewritten in volumetric form. A prescription for assigning forces to the Stokeslets comprising the swarm incorporates the action of interfacial tension without having to identify a boundary surface. Numerical simulations agree with linear small-deformation theory, and reproduce the spontaneous coalescense of two touching drops.

  2. Monitoring of interfacial tensions by drop counting

    SciTech Connect

    Duerksen, W.K.; Boring, C.P.; McLaughlin, J.F.; Harless, D.P.

    1988-11-01

    A capillary tube device was shown to provide a rapid means of measuring the interfacial tension between water and Freon-113. The measurement technique is based on counting the number of drops that form when a fixed volume of water passes through the capillary tube into the bulk Freon. The interfacial tension is predicted to be proportional to the number of drops to the negative 2/3 power. Calibration curves were obtained for Freon-water samples containing known concentrations of a surfactant. A standard Gibbs adsorption curve was obtained. 5 refs., 3 figs., 2 tabs.

  3. Complications of sodium hydroxide chemical matrixectomy: nail dystrophy, allodynia, hyperalgesia.

    PubMed

    Bostancı, Seher; Koçyiğit, Pelin; Güngör, Hilayda Karakök; Parlak, Nehir

    2014-11-01

    Ingrown toenails are seen most commonly in young adults, and they can seriously affect daily life. Partial nail avulsion with chemical matrixectomy, generally by using either sodium hydroxide or phenol, is one of the most effective treatment methods. Known complications of phenol matrixectomy are unpredictable tissue damage, prolonged postoperative drainage, increased secondary infection rates, periostitis, and poor cosmetic results. To our knowledge, there have been no reports about the complications related to sodium hydroxide matrixectomy. Herein, we describe three patients who developed nail dystrophy, allodynia, and hyperalgesia after sodium hydroxide matrixectomy.

  4. Nonaborane and decaborane cluster anions can enhance the ignition delay in hypergolic ionic liquids and induce hypergolicity in molecular solvents.

    PubMed

    McCrary, Parker D; Barber, Patrick S; Kelley, Steven P; Rogers, Robin D

    2014-05-01

    The dissolution of nido-decaborane, B10H14, in ionic liquids that are hypergolic (fuels that spontaneously ignite upon contact with an appropriate oxidizer), 1-butyl-3-methylimidazolium dicyanamide, 1-methyl-4-amino-1,2,4-triazolium dicyanamide, and 1-allyl-3-methylimidazolium dicyanamide, led to the in situ generation of a nonaborane cluster anion, [B9H14](-), and reductions in ignition delays for the ionic liquids suggesting salts of borane anions could enhance hypergolic properties of ionic liquids. To explore these results, four salts based on [B10H13](-) and [B9H14](-), triethylammonium nido-decaborane, tetraethylammonium nido-decaborane, 1-ethyl-3-methylimidazolium arachno-nonaborane, and N-butyl-N-methyl-pyrrolidinium arachano-nonaborane were synthesized from nido-decaborane by reaction of triethylamine or tetraethylammonium hydroxide with nido-decaborane in the case of salts containing the decaborane anion or via metathesis reactions between sodium nonaborane (Na[B9H14]) and the corresponding organic chloride in the case of the salts containing the nonaborane anion. These borane cluster anion salts form stable solutions in some combustible polar aprotic solvents such as tetrahydrofuran and ethyl acetate and trigger hypergolic reactivity of these solutions. Solutions of these salts in polar protic solvents are not hypergolic. PMID:24716643

  5. Cd(II)-coordination framework: synthesis, anion-induced structural transformation, anion-responsive luminescence, and anion separation.

    PubMed

    Hou, Shan; Liu, Qi-Kui; Ma, Jian-Ping; Dong, Yu-Bin

    2013-03-18

    A series of Cd(II) coordination frameworks that are constructed from a new oxadiazole-bridged ligand 3,5-bis(3-pyridyl-3-(3'-methylphenyl)-1,3,4-oxadiazole (L) and CdX2 (X = NO3(-), Cl(-), Br(-), I(-), N3(-), and SCN(-)) were synthesized. The NO3(-) anion of the solid CdL2(NO3)2·2THF (1) is able to be quantitatively exchanged with Cl(-), Br(-), I(-), SCN(-), and N3(-) in the solid state. For Cl(-) and Br(-), the anion exchange resulted in a anion-induced structural transformation to form the structures of 2 and 3, respectively. In addition, the Cd(II) structure herein exhibits the anion-responsive photoluminescence, which could be a useful method to monitor the anion-exchange process. Notably, compound 1 can recognize and completely separate SCN(-)/N3(-) with similar geometry.

  6. Gamma radiation effect on gas production in anion exchange resins

    NASA Astrophysics Data System (ADS)

    Traboulsi, A.; Labed, V.; Dauvois, V.; Dupuy, N.; Rebufa, C.

    2013-10-01

    Radiation-induced decomposition of Amberlite IRA400 anion exchange resin in hydroxide form by gamma radiolysis has been studied at various doses in different atmospheres (anaerobic, anaerobic with liquid water, and aerobic). The effect of these parameters on the degradation of ion exchange resins is rarely investigated in the literature. We focused on the radiolysis gases produced by resin degradation. When the resin was irradiated under anaerobic conditions with liquid water, the liquid phase over the resin was also analyzed to identify any possible water-soluble products released by degradation of the resin. The main products released are trimethylamine (TMA), molecular hydrogen (H2g) and carbon dioxide (CO2g). TMA and H2g are produced in all the irradiation atmospheres. However, TMA was in gaseous form under anaerobic and aerobic conditions and in aqueous form in presence of liquid water. In the latter conditions, TMAaq was associated with aqueous dimethylamine (DMAaq), monomethylamine (MMAaq) and ammonia (NH). CO2g is formed in the presence of oxygen due to oxidation of organic compounds present in the system, in particular the degradation products such as TMAg.

  7. Anion-exchange sorption of molybdate and germanate

    SciTech Connect

    Kislinskaya, G.E.; Denisova, T.I.; Sheka, I.A.

    1983-07-20

    Interest in sorption of molybdenum and germanium from salt solutions is prompted by industrial requirements related to purification of such solutions and also to extraction of these elements from various industrial liquors.In order to identify the ionic forms of molybdenum and germanium having the highest sorption activity and to determine the optimal conditions for extraction of these elements from solutions with high electrolyte contents, we studied the states of molybdenum(VI) and germanium(IV) in solutions of sodium chloride in various concentrations, and sorption of these elements by strongly basic macroporous anion-exchange resins and by iron and aluminum hydroxides in relation to the pH, concentrations of the elements, and time of contact between the solution and the sorbent. Examination of literature data shows that the molecular and ionic states of these elements in the presence of high salt concentrations have been studied mainly in acidic solutions and at higher molybdenum and germanium concentrations. However, for selection of a method of removal of molybdenum and germanium from production liquors it is also necessary to have analogous information on their states when present in microconcentrations over wide ranges of pH.

  8. Homogeneous Precipitation of Nickel Hydroxide Powders

    SciTech Connect

    Bora Mavis

    2003-12-12

    Precipitation and characterization of nickel hydroxide powders were investigated. A comprehensive precipitation model incorporating the metal ion hydrolysis, complexation and precipitation reactions was developed for the production of the powders with urea precipitation method. Model predictions on Ni{sup 2+} precipitation rate were confirmed with precipitation experiments carried out at 90 C. Experimental data and model predictions were in remarkable agreement. Uncertainty in the solubility product data of nickel hydroxides was found to be the large contributor to the error. There were demonstrable compositional variations across the particle cross-sections and the growth mechanism was determined to be the aggregation of primary crystallites. This implied that there is a change in the intercalate chemistry of the primary crystallites with digestion time. Predicted changes in the concentrations of simple and complex ions in the solution support the proposed mechanism. The comprehensive set of hydrolysis reactions used in the model described above allows the investigation of other systems provided that accurate reaction constants are available. the fact that transition metal ions like Ni{sup 2+} form strong complexes with ammonia presents a challenge in the full recovery of the Ni{sup 2+}. On the other hand, presence of Al{sup 3+} facilitates the complete precipitation of Ni{sup 2+} in about 3 hours of digestion. A challenge in their predictive modeling studies had been the fact that simultaneous incorporation of more than one metal ion necessitates a different approach than just using the equilibrium constants of hydrolysis, complexation and precipitation reactions. Another limitation of using equilibrium constants is that the nucleation stage of digestion, which is controlled mainly by kinetics, is not fully justified. A new program released by IBM Almaden Research Center (Chemical Kinetics Simulator{trademark}, Version 1.01) lets the user change the order of

  9. The Constrained Vapor Bubble Experiment - Interfacial Flow Region

    NASA Technical Reports Server (NTRS)

    Kundan, Akshay; Wayner, Peter C., Jr.; Plawsky, Joel L.

    2015-01-01

    Internal heat transfer coefficient of the CVB correlated to the presence of the interfacial flow region. Competition between capillary and Marangoni flow caused Flooding and not a Dry-out region. Interfacial flow region growth is arrested at higher power inputs. 1D heat model confirms the presence of interfacial flow region. 1D heat model confirms the arresting phenomena of interfacial flow region Visual observations are essential to understanding.

  10. Tripodal Receptors for Cation and Anion Sensors

    PubMed Central

    Kuswandi, Bambang; Nuriman; Verboom, Willem; Reinhoudt, David N.

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selective recognition and sensing of cations and anions. Examples on the relationship between structure and selectivity towards cations and anions are described. Furthermore, their applications as potentiometric ion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  11. An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting.

    PubMed

    Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G; Duan, Xue

    2015-07-15

    In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm(2) at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting.

  12. Enhancing phosphate adsorption by Mg/Al layered double hydroxide functionalized biochar with different Mg/Al ratios.

    PubMed

    Li, Ronghua; Wang, Jim J; Zhou, Baoyue; Awasthi, Mukesh Kumar; Ali, Amjad; Zhang, Zengqiang; Gaston, Lewis A; Lahori, Altaf Hussain; Mahar, Amanullah

    2016-07-15

    Mg/Al ratio plays a significant role for anion adsorption by Mg/Al-layered double hydroxides (Mg/Al-LDHs) modified biochar. In this study, Mg/Al-LDHs biochar with different Mg/Al ratios (2, 3, 4) were prepared by co-precipitation for phosphate removal from aqueous solution. Factors on phosphate adsorption including Mg/Al ratio, pH, and the presence of other inorganic anions were investigated through batch experiments. Increasing Mg/Al ratio in the Mg/Al-LDHs biochar composites generally enhanced phosphate adsorption with Langmuir adsorption maximum calculated at 81.83mg phosphorous (P) per gram of 4:1Mg/Al-LDHs biochar at pH3.0. The adsorption process was best described by the pseudo-second-order kinetic model. Solution pH had greater effects on the phosphate adsorption by Mg/Al LDHs biochar composites with lower Mg/Al ratios. The presence of other inorganic anions decreased the phosphate adsorption efficiency in the order of F(-) > SO4(2-) > NO2(-) >Cl(-). Phosphate adsorption mechanism involves ion exchange, electrostatic attraction and surface inner-sphere complex formation. Overall, Mg/Al-LDHs biochar composites offer a potential alternative of carbon-based adsorbent for phosphate removal from aqueous solution. PMID:27058131

  13. An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

    PubMed Central

    Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

    2015-01-01

    In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting. PMID:26174201

  14. Atomic resolution mapping of interfacial intermixing and segregation in InAs/GaSb superlattices: A correlative study

    SciTech Connect

    Kim, Honggyu; Meng Yifei; Zuo Jianmin; Rouviere, Jean-Luc

    2013-03-14

    We combine quantitative analyses of Z-contrast images with composition analyses employing atom probe tomography (APT) correlatively to provide a quantitative measurement of atomic scale interfacial intermixing in an InAs/GaSb superlattice (SL). Contributions from GaSb and InAs in the Z-contrast images are separated using an improved image processing technique. Correlation with high resolution APT composition analyses permits an examination of interfacial segregation of both cations and anions and their incorporation in the short period InAs/GaSb SL. Results revealed short, intermediate, and long-range intermixing of In, Ga, and Sb during molecular beam epitaxial growth and their distribution in the SL.

  15. Hydroxide-Assisted Bonding of Ultra-Low-Expansion Glass

    NASA Technical Reports Server (NTRS)

    Abramovici, Alexander; White, Victor

    2008-01-01

    A process for hydroxide-assisted bonding has been developed as a means of joining optical components made of ultra-low-expansion (ULE) glass, while maintaining sufficiently precise alignment between. The process is intended mainly for use in applications in which (1) bonding of glass optical components by use of epoxy does not enable attainment of the required accuracy and dimensional stability and (2) conventional optical contacting (which affords the required accuracy and stability) does not afford adequate bond strength. The basic concept of hydroxide-assisted bonding is not new. The development of the present process was prompted by two considerations: (1) The expertise in hydroxide-assisted bonding has resided in very few places and the experts have not been willing to reveal the details of their processes and (2) data on the reliability and strength attainable by hydroxide-assisted bonding have been scarce.

  16. 68. INTERIOR VIEW LOOKING OF THE CAUSTIC SODA (SODIUM HYDROXIDE) ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    68. INTERIOR VIEW LOOKING OF THE CAUSTIC SODA (SODIUM HYDROXIDE) BUILDING, LOOKING AT CAUSTIC SODA MEASURING TANKS. (DATE UNKNOWN). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  17. 21 CFR 73.2326 - Chromium hydroxide green.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2326 Chromium hydroxide green. (a) Identity and... in coloring externally applied cosmetics, including those intended for use in the area of the eye,...

  18. 21 CFR 73.2326 - Chromium hydroxide green.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2326 Chromium hydroxide green. (a) Identity and... in coloring externally applied cosmetics, including those intended for use in the area of the eye,...

  19. 21 CFR 73.2326 - Chromium hydroxide green.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2326 Chromium hydroxide green. (a) Identity and... in coloring externally applied cosmetics, including those intended for use in the area of the eye,...

  20. Conversion coatings prepared or treated with calcium hydroxide solutions

    NASA Technical Reports Server (NTRS)

    Minevski, Zoran (Inventor); Clarke, Eric (Inventor); Maxey, Jason (Inventor); Nelson, Carl (Inventor); Eylem, Cahit (Inventor)

    2002-01-01

    A conversion coating process that forms a stable and corrosion-resistant oxide layer on metal or metal oxide substrates or layers. Particularly, the conversion coating process involves contacting the metal or metal oxide substrate or layer with the aqueous calcium hydroxide solutions in order to convert the surface of the substrate to a stable metal oxide layer or coating. According to the present invention, the calcium hydroxide solution is prepared by removing carbon dioxide from water or an aqueous solution before introducing the calcium hydroxide. In this manner, formation of calcium carbonate particles is avoided and the porosity of the conversion coating produced by the calcium hydroxide solution is reduced to below about 1%.

  1. Gels based on anion recognition between triurea receptor and phosphate anion.

    PubMed

    Yang, Cuiling; Wu, Biao; Chen, Yongming; Zhang, Ke

    2015-04-01

    Anion recognition between the triurea receptor and phosphate anion is demonstrated as the cross-linkage to build supramolecular polymer gels for the first time. A novel multi-block copolymer (3) is designed to have functional triurea groups as cross-linking units along the polymer main chain. By virtue of anion coordination between the triurea receptor and phosphate anion with a binding mode of 2:1, supramolecular polymer gels are then prepared based on anion recognition using 3 as the building block. PMID:25694389

  2. Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

    PubMed Central

    Rambo, Brett M.; Silver, Eric S.; Bielawski, Christopher W.; Sessler, Jonathan L.

    2010-01-01

    This chapter covers recent advances in the development of polymeric materials containing discrete heterocyclic anion receptors, and focuses on advances in anion binding and chemosensor chemistry. The development of polymers specific for anionic species is a relatively new and flourishing area of materials chemistry. The incorporation of heterocyclic receptors capable of complexing anions through non-covalent interactions (e.g., hydrogen bonding and electrostatic interactions) provides a route to not only sensitive but also selective polymer materials. Furthermore, these systems have been utilized in the development of polymers capable of extracting anionic species from aqueous environments. These latter materials may lead to advances in water purification and treatment of diseases resulting from surplus ions. PMID:20871791

  3. Picosecond dynamics of benzophenone anion solvation

    SciTech Connect

    Lin, Y.; Jonah, C.D. )

    1993-01-14

    The dynamics of benzophenone anion solvation in alcohols are studied by pulse-radiolysis techniques. The solvation process is characterized by the blue shift of the transient absorption spectrum of the anion and is faster for the smaller alcohols. The anion is solvated more slowly than the electron in the same solvent, but the solvation times of both are similar to [tau][sub 2], the solvent dielectric relaxation time. The familiar phenomenological two-state model of solvation was found to be inappropriate for describing the anion solvation process. A multistate process appears to be a more appropriate description. The authors modeled the kinetics of the spectral relaxation. In most cases, nearly quantitative agreement between the calculated and observed spectra is achieved. The characteristic relaxation times for the alcohol solvents around the anions were also reproduced. 50 refs., 8 figs., 3 tabs.

  4. Creating molecular macrocycles for anion recognition

    PubMed Central

    2016-01-01

    Summary The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures. PMID:27340452

  5. Solvent and process for recovery of hydroxide from aqueous mixtures

    DOEpatents

    Moyer, Bruce A.; Chambliss, C. Kevin; Bonnesen, Peter V.; Keever, Tamara J.

    2001-01-01

    Hydroxide values and associated alkali metal may be recovered from alkaline aqueous solutions using classes of fluorinated alcohols in a water immiscible solvent. The alcohols are characterized by fluorine substituents which are proximal to the acidic alcohol protons and are located to adjust the acidity of the extractant and the solubility of the extractant in the solvent. A method for stripping the extractant and solvent to regenerate the extractant and purified aqueous hydroxide solution is described.

  6. Development of high-speed reactive processing system for carbon fiber-reinforced polyamide-6 composite: In-situ anionic ring-opening polymerization

    NASA Astrophysics Data System (ADS)

    Kim, Sang-Woo; Seong, Dong Gi; Yi, Jin-Woo; Um, Moon-Kwang

    2016-05-01

    In order to manufacture carbon fiber-reinforced polyamide-6 (PA-6) composite, we optimized the reactive processing system. The in-situ anionic ring-opening polymerization of ɛ-caprolactam was utilized with proper catalyst and initiator for PA-6 matrix. The mechanical properties such as tensile strength, inter-laminar shear strength and compressive strength of the produced carbon fiber-reinforced PA-6 composite were measured, which were compared with the corresponding scanning electron microscope (SEM) images to investigate the polymer properties as well as the interfacial interaction between fiber and polymer matrix. Furthermore, kinetics of in-situ anionic ring-opening polymerization of ɛ-caprolactam will be discussed in the viewpoint of increasing manufacturing speed and interfacial bonding between PA-6 matrix and carbon fiber during polymerization.

  7. Sodium-hydroxide solution treatment on sandstone cores

    SciTech Connect

    Lee, S.J.

    1984-01-01

    This research was performed to study the effect of sodium hydroxide solution on the sandstone core samples and to develop a method whereby the permeability of the samples could be increased by the injection of sodium hydroxide solution. This work should provide the first step in developing a technique that can be used in the stimulation of oil and gas wells. A series of tests was conducted in which sodium hydroxide solution with concentrations ranging from 0.25 N to 2.00 N was injected into a number of Berea sandstone cores. The tests were conducted at room temperature and at 180{degree}F. In some cases the core sample were damaged by the injection of fresh water which resulted in a marked reduction in the permeability of the cores prior to the injection of sodium hydroxide solution. Based on laboratory testing with measurements of uniaxial compressive strength, SEM examination and X-ray analysis, it was found that sodium hydroxide interacted with sandstone to promote (1) partial dissolution of the sandstone minerals; (2) sandstone weight loss; (3) increased porosity; (4) weakening of the sandstone cores; and (5) changes in permeability. The interaction increased with increasing temperature and increasing sodium hydroxide concentration. However, at concentrations higher than 1.00 N, the degree of increase in permeability was not as large even though the sandstone weight loss and the increase in porosity did increase.

  8. The role of calcium hydroxide in the formation of thaumasite

    SciTech Connect

    Bellmann, F. Stark, J.

    2008-10-15

    It has recently been derived by thermodynamic calculation that the presence or absence of calcium hydroxide plays a vital role in the resistance of cement paste or concrete against the formation of thaumasite. To obtain experimental data on this matter, special binders have been mixed and used for the preparation of mortar bars. These specimens were exposed to moderate sulphate attack for a period of 18 months at a temperature of 8 deg. C. Mortar bars containing calcium hydroxide showed visual signs of attack a few months after exposure, leading to expansion, mass loss and complete failure. In contrast to this, no signs of attack were observed when no calcium hydroxide was present in the microstructure. These results confirm the conclusions of earlier thermodynamic calculations that the presence of calcium hydroxide has an important impact on the formation of thaumasite. Calcium-rich C-S-H formed in the presence of calcium hydroxide is vulnerable against sulphate attack and the formation of thaumasite. In the absence of calcium hydroxide, C-S-H has a much lower calcium/silicon ratio and a higher resistance against the formation of thaumasite.

  9. Interfacial ion-transfer mechanism for the intense luminescence observed when opening self-seal envelopes.

    PubMed

    Alexander, Andrew J

    2012-09-18

    The unusually intense luminescence (commonly called triboluminescence) observed when opening self-seal envelopes has been studied using spectroscopy. Emissions from gas-phase species due to electrical discharge were observed, which in the case of air consists of vibronic transitions of N(2)(C(3)Π(u)-B(3)Π(g)) in the ultraviolet (UV) region (280-400 nm). However, the major cause of the intense blue luminescence (around 435 nm) is attributed to optical brightening agents added to the white paper. The results suggest that the emission from the brightening agents may be caused by two mechanisms: (i) fluorescence due to excitation by the UV light from the gas discharge and (ii) nonoptically, by electron transfer. The electrical discharge results from contact electrification; we propose a mechanism for the charge transfer involving a net migration of hydroxide anions out of the paper into the wet latex-adhesive during drying. PMID:22924818

  10. Separation of alditols of interest in food products by high-performance anion-exchange chromatography with pulsed amperometric detection.

    PubMed

    Corradini, C; Canali, G; Cogliandro, E; Nicoletti, I

    1997-12-12

    High-performance anion-exchange chromatography (HPAEC)-pulsed amperometric detection (PAD) employing a CarboPac MA 1 column was investigated with respect to mobile phase composition, linear response characteristics, repeatability, reproducibility and sensitivity with different alditols used as sugar substitutes in food and confectionery products. The energy-reduced bulk sweeteners isomalt and maltitol were well resolved in less than 25 min by isocratic elution with 600 mM sodium hydroxide solution. HPAEC-PAD was also successfully applied to the determination of alditols in sugar-free products and a low-calorie sweetener containing sorbitol, mannitol and fructose at different levels.

  11. Charge screening between anionic and cationic surfactants in ionic liquids.

    PubMed

    Chen, Lang G; Bermudez, Harry

    2013-03-01

    The aggregation and interfacial behavior of mixtures of anionic (sodium dodecylsulfate, SDS) and cationic (dodecylammonium bromide, DTAB) surfactants were investigated. A room-temperature ionic liquid (IL) was explored as a solvent for the SDS/DTAB system and compared to water. The critical micelle concentration (cmc) and composition in mixed micelles were determined for both solvents. Our experiments showed nearly ideal mixing of SDS/DTAB over the entire composition range and suggest that charge screening is prominent in ILs. This behavior is in sharp contrast to the strong electrostatic attraction and a multiphase composition gap in water. Two models by Clint and Rubingh, which describe ideal and nonideal micellar behavior, respectively, are discussed on the basis of our results. According to Rubingh's model, the composition of mixed micelles is gradually changing with the bulk composition in ILs but tends to be a 1:1 ratio in water. The results here are further support of the strong charge screening in ionic liquids.

  12. Pseudo-hydroxide extraction in the separation of sodium hydroxide from aqueous solutions using alkyl phenols

    SciTech Connect

    Kang, Hyun Ah; Moyer, Bruce A

    2006-01-01

    Pseudo-hydroxide extraction of sodium hydroxide from aqueous solution using four alkyl phenols of nearly identical molecular weight in 1-octanol at 25 degrees C was examined to understand the effect of alkyl substituents. The order of extraction strength among the four alkyl phenols tested was 4-tert-octylphenol. 3,5-di-tertbutylphenol. 2,4-di-tert-butylphenol. 2,6-di-tert-butyl-4-methylphenol. A good correlation with phenol pK(a) was observed, indicating that extraction strength is determined by phenol acidity, as modified by steric effects in proximity to the phenol - OH group. The effective partition ratios (P-eff) of two phenols from 1 M NaOH solution were determined, showing that the phenols remain predominantly in the 1-octanol phase even when converted to their sodium salts. However, the hydrophobicity of the tested phenols may not be sufficient for process purposes. The equilibrium constants for the governing extraction equilibria were determined by modeling the data using the program SXLSQI, supporting the cation-exchange extraction mechanism. The proposed mechanism consists of two simple sets of equilibria for a. Ion-pair extraction to give Na+OH- ion pairs and corresponding free ions in 1-octanol the phase and b. Cation exchange by monomeric phenol molecules (HAs) to form monomeric organic-phase Na(+)A(-) ion pairs and corresponding free organic-phase ions.

  13. Synthesis of monodispersed hematite particles from highly concentrated metal hydroxide gels

    NASA Astrophysics Data System (ADS)

    Liu, Qingyuan

    The synthesis of uniform hematite particles with various morphologies from highly concentrated metal hydroxide gels was investigated. The investigations were focused on the effects of cation (trivalent and divalent), anions (arsenate and selenate), and organic additives (alkyl sufates) on particle formation. Monodispersed aluminum-substituted hematite particles were synthesized from concentrated mixed solutions of FeCl3 and AlCl3. With increasing aluminum contents, the product particles exhibited ellipsoidal, rod- and peanut-like shapes. Lattice parameter a decreased with increasing Al incorporation. The particles grew anisotropically along c crystal axis according to TEM and XRD analysis. Chromium substitution had a similar influence on particle shape modification. With increasing chromium content, hematite particles exhibited ellipsoidal and peanut-like morphologies. The incorporation of Cr in hematite increases with increasing Cr addition in the starting solution. The particles grew anisotropically along c crystal axis according to XRD analysis. The size of hematite particles decreased when divalent Cu or Mn contents increased in initial solutions. The cubic shape was well maintained with Cu addition. Hematite particles produced with the existence of Mn2+ were irregular in shape and porous in structure. Copper substitution in hematite was verified by both chemical analysis and lattice parameter calculation. However, the incorporation of Mn is negligible. Ellipsoidal and peanut-shaped hematite particles were synthesized with the addition of arsenate and selenate ions. Product particles were more elongated upon the addition of more anions. The shape modification effects of these anions were interpreted in terms of bond matching due to similar Fe-Fe and O-O distances of hematite and anions, respectively. The addition of alkyl sulfates produced peanut-shaped hematite particles. Uniform particles with the same morphology were always formed despite the differences in

  14. An ab initio molecular dynamics study of the liquid-vapor interface of an aqueous NaCl solution: inhomogeneous density, polarity, hydrogen bonds, and frequency fluctuations of interfacial molecules.

    PubMed

    Choudhuri, Jyoti Roy; Chandra, Amalendu

    2014-11-21

    We have presented a first principles simulation study of the structural and dynamical properties of a liquid-vapor interfacial system of a concentrated (5.3 M) aqueous NaCl solution. We have used ab initio molecular dynamics to examine the structural and dynamical properties of the bulk and interfacial regions. The structural aspects of the system that have been considered here include the inhomogeneous density profiles of ions and water molecules, hydrogen bond distributions, orientational profiles, and also vibrational frequency distributions in the bulk and interfacial regions. It is found that the sodium ions are mostly located in the interior, while the chloride anions occupy a significant portion of the interface of the slab. The water dipoles at the interface prefer to orient parallel to the surface. The dynamical aspects of the interfaces are investigated in terms of diffusion, orientational relaxation, hydrogen bond dynamics, and vibrational spectral diffusion. The results of the interfacial dynamics are compared with those of the corresponding bulk region. It is observed that the interfacial molecules exhibit faster diffusion and orientational relaxation with respect to the bulk. However, the interfacial molecules are found to have longer hydrogen bond lifetimes than those of the bulk. We have also investigated the correlations of hydrogen bond relaxation with the vibrational frequency fluctuations of interfacial water molecules.

  15. Effect of Rare Earth Ions on the Properties of Composites Composed of Ethylene Vinyl Acetate Copolymer and Layered Double Hydroxides

    PubMed Central

    Wang, Lili; Li, Bin; Zhao, Xiaohong; Chen, Chunxia; Cao, Jingjing

    2012-01-01

    Background The study on the rare earth (RE)-doped layered double hydroxides (LDHs) has received considerable attention due to their potential applications in catalysts. However, the use of RE-doped LDHs as polymer halogen-free flame retardants was seldom investigated. Furthermore, the effect of rare earth elements on the hydrophobicity of LDHs materials and the compatibility of LDHs/polymer composite has seldom been reported. Methodology/Principal Findings The stearate sodium surface modified Ni-containing LDHs and RE-doped Ni-containing LDHs were rapidly synthesized by a coprecipitation method coupled with the microwave hydrothermal treatment. The influences of trace amounts of rare earth ions La, Ce and Nd on the amount of water molecules, the crystallinity, the morphology, the hydrophobicity of modified Ni-containing LDHs and the adsorption of modifier in the surface of LDHs were investigated by TGA, XRD, TEM, contact angle and IR, respectively. Moreover, the effects of the rare earth ions on the interfacial compatibility, the flame retardancy and the mechanical properties of ethylene vinyl acetate copolymer (EVA)/LDHs composites were also explored in detail. Conclusions/Significance S-Ni0.1MgAl-La displayed more uniform dispersion and better interfacial compatibility in EVA matrix compared with other LDHs. Furthermore, the S-Ni0.1MgAl-La/EVA composite showed the best fire retardancy and mechanical properties in all composites. PMID:22693627

  16. Ordered mesoporous materials based on interfacial assembly and engineering.

    PubMed

    Li, Wei; Yue, Qin; Deng, Yonghui; Zhao, Dongyuan

    2013-10-01

    Ordered mesoporous materials have inspired prominent research interest due to their unique properties and functionalities and potential applications in adsorption, separation, catalysis, sensors, drug delivery, energy conversion and storage, and so on. Thanks to continuous efforts over the past two decades, great achievements have been made in the synthesis and structural characterization of mesoporous materials. In this review, we summarize recent progresses in preparing ordered mesoporous materials from the viewpoint of interfacial assembly and engineering. Five interfacial assembly and synthesis are comprehensively highlighted, including liquid-solid interfacial assembly, gas-liquid interfacial assembly, liquid-liquid interfacial assembly, gas-solid interfacial synthesis, and solid-solid interfacial synthesis, basics about their synthesis pathways, princples and interface engineering strategies.

  17. Simultaneous quantification of sinigrin, sinalbin, and anionic glucosinolate hydrolysis products in Brassica juncea and Sinapis alba seed extracts using ion chromatography.

    PubMed

    Popova, Inna E; Morra, Matthew J

    2014-11-01

    Although mustards such as Sinapis alba and Brassica juncea contain glucosinolates (sinalbin and sinigrin, respectively) that hydrolyze to form biopesticidal products, routine quality control methods to measure active ingredients in seed and seed meals are lacking. We present a simple and fast ion chromatography method for the simultaneous quantification of sinigrin, sinalbin, and anionic hydrolysis products in mustard seed to assess biological potency. Optimum conditions include isocratic elution with 100 mM NaOH at a flow rate of 0.9 mL/min on a 4 × 210 mm hydroxide-selective anion-exchange column. All anion analytes including sinigrin, sinalbin, SO4(2-), and SCN(-) yielded recoveries ranging from 83 to 102% and limits of detection ≤0.04 mM, with samples displaying little interference from plant matrix components. Sample preparation is minimized and analysis times are shortened to <90 min as compared with previous methods that took days and multiple instruments.

  18. Anion photoelectron imaging spectroscopy of glyoxal

    NASA Astrophysics Data System (ADS)

    Xue, Tian; Dixon, Andrew R.; Sanov, Andrei

    2016-09-01

    We report a photoelectron imaging study of the radical-anion of glyoxal. The 532 nm photoelectron spectrum provides the first direct spectroscopic determination of the adiabatic electron affinity of glyoxal, EA = 1.10 ± 0.02 eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy of the radical-anion is determined as VDE = 1.30 ± 0.04 eV. The reported EA and VDE values are attributed to the most stable (C2h symmetry) isomers of the neutral and the anion.

  19. Photoelectron spectroscopy of nitromethane anion clusters

    NASA Astrophysics Data System (ADS)

    Pruitt, Carrie Jo M.; Albury, Rachael M.; Goebbert, Daniel J.

    2016-08-01

    Nitromethane anion and nitromethane dimer, trimer, and hydrated cluster anions were studied by photoelectron spectroscopy. Vertical detachment energies, estimated electron affinities, and solvation energies were obtained from the photoelectron spectra. Cluster structures were investigated using theoretical calculations. Predicted detachment energies agreed with experiment. Calculations show water binds to nitromethane anion through two hydrogen bonds. The dimer has a non-linear structure with a single ionic Csbnd H⋯O hydrogen bond. The trimer has two different solvent interactions, but both involve the weak Csbnd H⋯O hydrogen bond.

  20. Ketoprofen as a photoinitiator for anionic polymerization.

    PubMed

    Wang, Yu-Hsuan; Wan, Peter

    2015-06-01

    A new photoinitiating system for anionic polymerization of acrylates based on the efficient photodecarboxylation of Ketoprofen (1) and the related derivatives 3 and 4 that generate the corresponding carbanion intermediates is presented. Carbanion intermediates are confirmed by deuterium incorporation in the trapped Michael adducts and by spectroscopic detection using laser flash photolysis (LFP). This novel anionic initiating system features excitation in the near UV and visible regions, potential characteristics of photocontrolled living polymerization, and metal-free photoinitiators generated from photoexcitation, different from typical anionic polymerization where the polymerizations are initiated by heat and strong base containing alkali metals.

  1. Effect of Different Surfactants on the Interfacial Behavior of the n-Hexane-Water System in the Presence of Silica Nanoparticles.

    PubMed

    Biswal, Nihar Ranjan; Rangera, Naveen; Singh, Jayant K

    2016-07-28

    This paper presents the effect of negatively charged silica nanoparticles (NPs) on the interfacial tension of the n-hexane-water system at variable concentrations of four different surfactants, viz., an anionic surfactant, sodium dodecyl sulfate (SDS), a cationic surfactant, cetyltrimethylammonium bromide (CTAB), and two nonionic surfactants, Tween 20 and Triton X-100 (TX-100). The presence of negatively charged silica nanoparticles is found to have a different effect depending on the type of surfactant. In the case of ionic surfactants, SDS and CTAB, silica NPs reduce the interfacial tension of the system. On the contrary, for nonionic surfactants, Tween 20 and TX-100, silica NPs increase the interfacial tension. The increasing/decreasing nature of the interfacial tension in the presence of NPs is well supported by the calculated surface excess concentrations. The diffusion kinetic control (DKC) and statistical rate theory (SRT) models are used to understand the behavior of dynamic interfacial tension of the surfactant-NP-oil-water system. The DKC model is found to describe the studied surfactant-NP-oil-water systems more aptly. PMID:27367433

  2. Computational Investigation of the First Solvation Shell Structure of Interfacial and Bulk Aqueous Chloride and Iodide Ions

    SciTech Connect

    Wick, Collin D.; Xantheas, Sotiris S.

    2009-04-02

    Molecular dynamics simulations with polarizable interaction potentials were carried out to understand the solvation structure of chloride and iodide anions in bulk and interfacial water, showing qualitative similarities between the first solvation shell structures at the interface and bulk. For the more polarizable iodide, its solvation structure was more anisotropic than chloride, and this trend persisted at both the interface and in the bulk. Furthermore it was found that the first few clusters of water with iodide were quite different than the corresponding ones with chloride, with the former exhibiting more anisotropic configurations than the latter. The anisotropy of the solvation structure correlated with polarizability, but it was also found to inversely correlate with anion size. When polarizability was reduced to near zero, a very small anisotropy in the water solvation structure around the ion still persisted. Polarizable anions were found to have on average an induced dipole in the bulk that was significantly larger than zero. This induced dipole resulted in the water hydrogen atoms having stronger interactions with the anions on one side of them, in which the dipole was pointing at. In contrast, the other side of the anions, in which the induced dipole was pointing away from, had fewer water molecules present and, for the case of iodide, was rather devoid of water molecules all together at both the interface and in the bulk. This region formed a small cavity in the bulk, while at the air-water interface was simply part of the air interface. In the bulk, this small cavity may be viewed as somewhat hydrophobic, and the need for the extinction of this cavity may be one of the major driving forces for polarizable anions to reside at the air-water interface. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  3. Mesoscale Interfacial Dynamics in Magnetoelectric Nanocomposites

    SciTech Connect

    Shashank, Priya

    2009-12-14

    Biphasic composites are the key towards achieving enhanced magnetoelectric response. In order understand the control behavior of the composites and resultant symmetry of the multifunctional product tensors, we need to synthesized model material systems with the following features (i) interface formation through either deposition control or natural decomposition; (ii) a very high interphase-interfacial area, to maximize the ME coupling; and (iii) an equilibrium phase distribution and morphology, resulting in preferred crystallographic orientation relations between phases across the interphase-interfacial boundaries. This thought process guided the experimental evolution in this program. We initiated the research with the co-fired composites approach and then moved on to the thin film laminates deposited through the rf-magnetron sputtering and pulsed laser deposition process

  4. The contact area dependent interfacial thermal conductance

    SciTech Connect

    Liu, Chenhan; Wei, Zhiyong; Bi, Kedong; Yang, Juekuan; Chen, Yunfei; Wang, Jian

    2015-12-15

    The effects of the contact area on the interfacial thermal conductance σ are investigated using the atomic Green’s function method. Different from the prediction of the heat diffusion transport model, we obtain an interesting result that the interfacial thermal conductance per unit area Λ is positively dependent on the contact area as the area varies from a few atoms to several square nanometers. Through calculating the phonon transmission function, it is uncovered that the phonon transmission per unit area increases with the increased contact area. This is attributed to that each atom has more neighboring atoms in the counterpart of the interface with the increased contact area, which provides more channels for phonon transport.

  5. Frontiers of interfacial water research :workshop report.

    SciTech Connect

    Cygan, Randall Timothy; Greathouse, Jeffery A.

    2005-10-01

    Water is the critical natural resource of the new century. Significant improvements in traditional water treatment processes require novel approaches based on a fundamental understanding of nanoscale and atomic interactions at interfaces between aqueous solution and materials. To better understand these critical issues and to promote an open dialog among leading international experts in water-related specialties, Sandia National Laboratories sponsored a workshop on April 24-26, 2005 in Santa Fe, New Mexico. The ''Frontiers of Interfacial Water Research Workshop'' provided attendees with a critical review of water technologies and emphasized the new advances in surface and interfacial microscopy, spectroscopy, diffraction, and computer simulation needed for the development of new materials for water treatment.

  6. Interfacial geometry dictates cancer cell tumorigenicity

    NASA Astrophysics Data System (ADS)

    Lee, Junmin; Abdeen, Amr A.; Wycislo, Kathryn L.; Fan, Timothy M.; Kilian, Kristopher A.

    2016-08-01

    Within the heterogeneous architecture of tumour tissue there exists an elusive population of stem-like cells that are implicated in both recurrence and metastasis. Here, by using engineered extracellular matrices, we show that geometric features at the perimeter of tumour tissue will prime a population of cells with a stem-cell-like phenotype. These cells show characteristics of cancer stem cells in vitro, as well as enhanced tumorigenicity in murine models of primary tumour growth and pulmonary metastases. We also show that interfacial geometry modulates cell shape, adhesion through integrin α5β1, MAPK and STAT activity, and initiation of pluripotency signalling. Our results for several human cancer cell lines suggest that interfacial geometry triggers a general mechanism for the regulation of cancer-cell state. Similar to how a growing tumour can co-opt normal soluble signalling pathways, our findings demonstrate how cancer can also exploit geometry to orchestrate oncogenesis.

  7. Interfacial transport in lithium-ion conductors

    NASA Astrophysics Data System (ADS)

    Shaofei, Wang; Liquan, Chen

    2016-01-01

    Physical models of ion diffusion at different interfaces are reviewed. The use of impedance spectroscopy (IS), nuclear magnetic resonance (NMR), and secondary ion mass spectrometry (SIMS) techniques are also discussed. The diffusion of ions is fundamental to the operation of lithium-ion batteries, taking place not only within the grains but also across different interfaces. Interfacial ion transport usually contributes to the majority of the resistance in lithium-ion batteries. A greater understanding of the interfacial diffusion of ions is crucial to improving battery performance. Project supported by the Beijing S&T Project, China (Grant No. Z13111000340000), the National Natural Science Foundation of China (Grant Nos. 51325206 and 11234013) and the National Basic Research Program of China (Grant No. 2012CB932900).

  8. Scaling for interfacial tensions near critical endpoints.

    PubMed

    Zinn, Shun-Yong; Fisher, Michael E

    2005-01-01

    Parametric scaling representations are obtained and studied for the asymptotic behavior of interfacial tensions in the full neighborhood of a fluid (or Ising-type) critical endpoint, i.e., as a function both of temperature and of density/order parameter or chemical potential/ordering field. Accurate nonclassical critical exponents and reliable estimates for the universal amplitude ratios are included naturally on the basis of the "extended de Gennes-Fisher" local-functional theory. Serious defects in previous scaling treatments are rectified and complete wetting behavior is represented; however, quantitatively small, but unphysical residual nonanalyticities on the wetting side of the critical isotherm are smoothed out "manually." Comparisons with the limited available observations are presented elsewhere but the theory invites new, searching experiments and simulations, e.g., for the vapor-liquid interfacial tension on the two sides of the critical endpoint isotherm for which an amplitude ratio -3.25+/-0.05 is predicted.

  9. Interfacial chemistry in solvent extraction systems

    SciTech Connect

    Neuman, R.D.

    1993-01-01

    Research this past year continued to emphasize characterization of the physicochemical nature of the microscopic interfaces, i.e., reversed micelles and other association microstructures, which form in both practical and simplified acidic organophosphorus extraction systems associated with Ni, Co, and Na in order to improve on the model for aggregation of metal-extractant complexes. Also, the macroscopic interfacial behavior of model extractant (surfactant) molecules was further investigated. 1 fig.

  10. Interfacial chemistry in solvent extraction systems

    SciTech Connect

    Neuman, R.D.

    1992-01-01

    Research last year emphasized the nature of microscopic interfaces, i. e., reversed micelles and other association microstructures, which form in both practical and simplified acidic organophosphorus extraction systems associated with Ni, Co and Na in order to improve on a recently proposed model for aggregation of metal-extractant complexes. Also, the macroscopic interfacial behavior of extractant molecules and their interactions with metal ions which occur in hydrometallurgical solvent extraction systems were further investigated.

  11. Intrinsic interfacial phenomena in manganite heterostructures

    NASA Astrophysics Data System (ADS)

    Vaz, C. A. F.; Walker, F. J.; Ahn, C. H.; Ismail-Beigi, S.

    2015-04-01

    We review recent advances in our understanding of interfacial phenomena that emerge when dissimilar materials are brought together at atomically sharp and coherent interfaces. In particular, we focus on phenomena that are intrinsic to the interface and review recent work carried out on perovskite manganites interfaces, a class of complex oxides whose rich electronic properties have proven to be a useful playground for the discovery and prediction of novel phenomena.

  12. Interfacial microfluidic transport on micropatterned superhydrophobic textile.

    PubMed

    Xing, Siyuan; Jiang, Jia; Pan, Tingrui

    2013-05-21

    Textile-enabled interfacial microfluidics, utilizing fibrous hydrophilic yarns (e.g., cotton) to guide biological reagent flows, has been extended to various biochemical analyses recently. The restricted capillary-driving mechanism, however, persists as a major challenge for continuous and facilitated biofluidic transport. In this paper, we have first introduced a novel interfacial microfluidic transport principle to drive three-dimensional liquid flows on a micropatterned superhydrophobic textile (MST) platform in a more autonomous and controllable manner. Specifically, the MST system utilizes the surface tension-induced Laplace pressure to facilitate the liquid motion along the hydrophilic yarn, in addition to the capillarity present in the fibrous structure. The fabrication of MST is simply accomplished by stitching hydrophilic cotton yarn into a superhydrophobic fabric substrate (contact angle 140 ± 3°), from which well-controlled wetting patterns are established for interfacial microfluidic operations. The geometric configurations of the stitched micropatterns, e.g., the lengths and diameters of the yarn and bundled arrangement, can all influence the transport process, which is investigated both experimentally and theoretically. Two operation modes, discrete and continuous transport, are also presented in detail. In addition, the gravitational effect as well as the droplet removal process have been also considered and quantitatively analysed during the transport process. As a demonstration, an MST design has been implemented on an artificial skin surface to collect and remove sweat in a highly efficient and facilitated means. The results have illustrated that the novel interfacial transport on the textile platform can be potentially extended to a variety of biofluidic collection and removal applications.

  13. Interfacial chemistry and structure in ceramic composites

    SciTech Connect

    Jones, R.H.; Saenz, N.T.; Schilling, C.H.

    1990-09-01

    The interfacial chemistry and structure of ceramic matrix composites (CMCs) play a major role in the properties of these materials. Fiber-matrix interfaces chemistries are vitally important in the fracture strength, fracture toughness, and fracture resistance of ceramic composites because they influence fiber loading and fiber pullout. Elevated-temperature properties are also linked to the interfacial characteristics through the chemical stability of the interface in corrosive environments and the creep/pullout behavior of the interface. Physical properties such as electrical and thermal conductivity are also dependent on the interface. Fiber-matrix interfaces containing a 1-{mu}m-thick multilayered interface with amorphous and graphitic C to a 1-nm-thick SiO{sub 2} layer can result from sintering operations for some composite systems. Fibers coated with C, BN, C/BC/BN, and Si are also used to produce controlled interface chemistries and structures. Growth interfaces within the matrix resulting from processing of CMCs can also be crucial to the behavior of these materials. Evaluation of the interfacial chemistry and structure of CMCs requires the use of a variety of analytical tools, including optical microscopy, scanning electron microscopy, Auger electron spectroscopy, and transmission electron microscopy coupled with energy dispersive x-ray analysis. A review of the interfacial chemistry and structure of SiC whisker- and fiber-reinforced Si{sub 3}N{sub 4} and SiC/SiC materials is presented. Where possible, correlations with fracture properties and high-temperature stability are made. 94 refs., 10 figs.

  14. Microstructural Evolution Based on Fundamental Interfacial Properties

    SciTech Connect

    A. D. Rollett; D. J. Srolovitz; A. Karma

    2003-07-11

    This first CMSN project has been operating since the summer of 1999. The main achievement of the project was to bring together a community of materials scientists, physicists and mathematicians who share a common interest in the properties of interfaces and the impact of those properties on microstructural evolution. Six full workshops were held at Carnegie Mellon (CMU), Northwestern (NWU), Santa Fe, Northeastern University (NEU), National Institute for Standards and Technology (NIST), Ames Laboratory, and at the University of California in San Diego (UCSD) respectively. Substantial scientific results were obtained through the sustained contact between the members of the project. A recent issue of Interface Science (volume 10, issue 2/3, July 2002) was dedicated to the output of the project. The results include: the development of methods for extracting anisotropic boundary energy and mobility from molecular dynamics simulations of solid/liquid interfaces in nickel; the extraction of anisotropic energies and mobilities in aluminum from similar MD simulations; the application of parallel computation to the calculation of interfacial properties; the development of a method to extract interfacial properties from the fluctuations in interface position through consideration of interfacial stiffness; the use of anisotropic interface properties in studies of abnormal grain growth; the discovery of abnormal grain growth from random distributions of orientation in subgrain networks; the direct comparison at the scale of individual grains between experimentally observed grain growth and simulations, which confirmed the importance of including anisotropic interfacial properties in the simulations; the classification of a rich variety of dendritic morphologies based on slight variations in the anisotropy of the solid-liquid interface; development of phase field methods that permit both solidification and grain growth to be simulated within the same framework.

  15. Kinetics and mechanism of exogenous anion exchange in FeFbpA-NTA: significance of periplasmic anion lability and anion binding activity of ferric binding protein A.

    PubMed

    Heymann, Jared J; Gabricević, Mario; Mietzner, Timothy A; Crumbliss, Alvin L

    2010-02-01

    The bacterial transferrin ferric binding protein A (FbpA) requires an exogenous anion to facilitate iron sequestration, and subsequently to shuttle the metal across the periplasm to the cytoplasmic membrane. In the diverse conditions of the periplasm, numerous anions are known to be present. Prior in vitro experiments have demonstrated the ability of multiple anions to fulfill the synergistic iron-binding requirement, and the identity of the bound anion has been shown to modulate important physicochemical properties of iron-bound FbpA (FeFbpA). Here we address the kinetics and mechanism of anion exchange for the FeFbpA-nitrilotriacetate (NTA) assembly with several biologically relevant anions (citrate, oxalate, phosphate, and pyrophosphate), with nonphysiologic NTA serving as a representative synergistic anion/chelator. The kinetic data are consistent with an anion-exchange process that occurs in multiple steps, dependent on the identity of both the entering anion and the leaving anion. The exchange mechanism may proceed either as a direct substitution or through an intermediate FeFbpA-X* assembly based on anion (X) identity. Our kinetic results further develop an understanding of exogenous anion lability in the periplasm, as well as address the final step of the iron-free FbpA (apo-FbpA)/Fe(3+) sequestration mechanism. Our results highlight the kinetic significance of the FbpA anion binding site, demonstrating a correlation between apo-FbpA/anion affinity and the FeFbpA rate of anion exchange, further supporting the requirement of an exogenous anion to complete tight sequestration of iron by FbpA, and developing a mechanism for anion exchange within FeFbpA that is dependent on the identity of both the entering anion and the leaving anion. PMID:19813031

  16. Alkali Metal Salts with Designable Aryltrifluoroborate Anions.

    PubMed

    Iwasaki, Kazuki; Yoshii, Kazuki; Tsuzuki, Seiji; Matsumoto, Hajime; Tsuda, Tetsuya; Kuwabata, Susumu

    2016-09-01

    Aryltrifluoroborate ([ArBF3](-)) has a designable basic anion structure. Various [ArBF3](-)-based anions were synthesized to create novel alkali metal salts using a simple and safe process. Nearly 40 novel alkali metal salts were successfully obtained, and their physicochemical characteristics, particularly their thermal properties, were elucidated. These salts have lower melting points than those of simple inorganic alkali halide salts, such as KCl and LiCl, because of the weaker interactions between the alkali metal cations and the [ArBF3](-) anions and the anions' larger entropy. Moreover, interestingly, potassium cations were electrochemically reduced in the potassium (meta-ethoxyphenyl)trifluoroborate (K[m-OEtC6H4BF3]) molten salt at 433 K. These findings contribute substantially to furthering molten salt chemistry, ionic liquid chemistry, and electrochemistry. PMID:27510799

  17. Toxicity of triphenyltin hydroxide to fish.

    PubMed

    Antes, Fabiane G; Becker, Alexssandro G; Parodi, Thaylise V; Clasen, Barbara; Lópes, Thais; Loro, Vania L; Baldisserotto, Bernardo; Flores, Erico M M; Dressler, Valderi L

    2013-11-01

    Triphenyltin (TPhT) is used worldwide in pesticide formulas for agriculture. Toxic effects of this compound to aquatic life have been reported; however, the biochemical response of fish exposed to different concentrations of TPhT hydroxide (TPhTH) was investigated for the first time in this study. The lethal concentration (LC50) of TPhTH to silver catfish, Rhamdia quelen, was calculated from an acute-exposure experiment (96 h). In addition, acethylcholinesterase (AChE) activity in brain and muscle-as well as glucose, glycogen, lactate, total protein, ammonia, and free amino acids in liver and muscle-were evaluated in a chronic-exposure experiment (15-day exposure). Speciation analysis of tin (Sn) was performed in fish tissues at the end of both experiments using gas chromatography coupled to a pulsed-flame photometric detector (GC-PFPD). Concentrations of TPhT, diphenyltin, and monophenyltin (reported as Sn) were lower than limits of quantification (10σ criteria). Waterborne TPhTH concentration used through the experiment was also evaluated by GC-PFPD, and no degradation of this species was observed. The LC50 value for silver catfish juveniles was 9.73 μg L(-1) (as Sn). Decreased brain and muscle AChE activities were observed in fish exposed to TPhTH in relation to unexposed fish (control). Liver glycogen and lactate levels were significantly higher in fish kept at the highest waterborne TPhTH concentration compared with the control. Liver and muscle glucose levels of fish exposed to all TPhTH concentrations were significantly lower than those of control fish. Silver catfish exposed to all TPhTH concentrations showed lower total protein values and higher total free amino acids levels in liver and muscle compared with controls. Total ammonia levels in liver and muscle were significantly higher for the highest TPhTH concentration compared with controls. In conclusion, TPhTH caused metabolic alterations in silver catfish juveniles, and the analyzed parameters can

  18. Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites

    NASA Astrophysics Data System (ADS)

    Nedim Ay, Ahmet; Konuk, Deniz; Zümreoglu-Karan, Birgul

    2011-12-01

    A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules.

  19. Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites

    PubMed Central

    2011-01-01

    A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules. PMID:21711652

  20. The structure of aqueous sodium hydroxide solutions: a combined solution x-ray diffraction and simulation study.

    PubMed

    Megyes, Tünde; Bálint, Szabolcs; Grósz, Tamás; Radnai, Tamás; Bakó, Imre; Sipos, Pál

    2008-01-28

    To determine the structure of aqueous sodium hydroxide solutions, results obtained from x-ray diffraction and computer simulation (molecular dynamics and Car-Parrinello) have been compared. The capabilities and limitations of the methods in describing the solution structure are discussed. For the solutions studied, diffraction methods were found to perform very well in describing the hydration spheres of the sodium ion and yield structural information on the anion's hydration structure. Classical molecular dynamics simulations were not able to correctly describe the bulk structure of these solutions. However, Car-Parrinello simulation proved to be a suitable tool in the detailed interpretation of the hydration sphere of ions and bulk structure of solutions. The results of Car-Parrinello simulations were compared with the findings of diffraction experiments.

  1. Interfacial Symmetry Control of Emergent Ferromagnetism

    NASA Astrophysics Data System (ADS)

    Grutter, Alexander; Borchers, Julie; Kirby, Brian; He, Chunyong; Arenholz, Elke; Vailionis, Arturas; Flint, Charles; Suzuki, Yuri

    Atomically precise complex oxide heterostructures provide model systems for the discovery of new emergent phenomena since their magnetism, structure and electronic properties are strongly coupled. Octahedral tilts and rotations have been shown to alter the magnetic properties of complex oxide heterostructures, but typically induce small, gradual magnetic changes. Here, we demonstrate sharp switching between ferromagnetic and antiferromagnetic order at the emergent ferromagnetic interfaces of CaRuO3/CaMnO3 superlattices. Through synchrotron X-ray diffraction and neutron reflectometry, we show that octahedral distortions in superlattices with an odd number of CaMnO3 unit cells in each layer are symmetry mismatched across the interface. In this case, the rotation symmetry switches across the interface, reducing orbital overlap, suppressing charge transfer from Ru to Mn, and disrupting the interfacial double exchange. This disruption switches half of the interfaces from ferromagnetic to antiferromagnetic and lowers the saturation magnetic of the superlattice from 1.0 to 0.5 μB/interfacial Mn. By targeting a purely interfacial emergent magnetic system, we achieve drastic alterations to the magnetic ground state with extremely small changes in layer thickness.

  2. Interfacial Studies of Sized Carbon Fiber

    SciTech Connect

    Shahrul, S. N.; Hartini, M. N.; Hilmi, E. A.; Nizam, A.

    2010-03-11

    This study was performed to investigate the influence of sizing treatment on carbon fiber in respect of interfacial adhesion in composite materials, Epolam registered 2025. Fortafil unsized carbon fiber was used to performed the experiment. The fiber was commercially surface treated and it was a polyacrylonitrile based carbon fiber with 3000 filament per strand. Epicure registered 3370 was used as basic sizing chemical and dissolved in two types of solvent, ethanol and acetone for the comparison purpose. The single pull out test has been used to determine the influence of sizing on carbon fiber. The morphology of carbon fiber was observed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The apparent interfacial strength IFSS values determined by pull out test for the Epicure registered 3370/ethanol sized carbon fiber pointed to a good interfacial behaviour compared to the Epicure registered 3370/acetone sized carbon fiber. The Epicure registered 3370/ethanol sizing agent was found to be effective in promoting adhesion because of the chemical reactions between the sizing and Epolam registered 2025 during the curing process. From this work, it showed that sized carbon fiber using Epicure registered 3370 with addition of ethanol give higher mechanical properties of carbon fiber in terms of shear strength and also provided a good adhesion between fiber and matrix compared to the sizing chemical that contain acetone as a solvent.

  3. Investigation of interfacial rheology & foam stability.

    SciTech Connect

    Yaklin, Melissa A.; Cote, Raymond O.; Grillet, Anne Mary; Walker, Lynn M.; Koehler, Timothy P.; Reichert, Matthew D.; Castaneda, Jaime N.; Mondy, Lisa Ann; Brooks, Carlton, F.

    2010-05-01

    The rheology at gas-liquid interfaces strongly influences the stability and dynamics of foams and emulsions. Several experimental techniques are employed to characterize the rheology at liquid-gas interfaces with an emphasis on the non-Newtonian behavior of surfactant-laden interfaces. The focus is to relate the interfacial rheology to the foamability and foam stability of various aqueous systems. An interfacial stress rheometer (ISR) is used to measure the steady and dynamic rheology by applying an external magnetic field to actuate a magnetic needle suspended at the interface. Results are compared with those from a double wall ring attachment to a rotational rheometer (TA Instruments AR-G2). Micro-interfacial rheology (MIR) is also performed using optical tweezers to manipulate suspended microparticle probes at the interface to investigate the steady and dynamic rheology. Additionally, a surface dilatational rheometer (SDR) is used to periodically oscillate the volume of a pendant drop or buoyant bubble. Applying the Young-Laplace equation to the drop shape, a time-dependent surface tension can be calculated and used to determine the effective dilatational viscosity of an interface. Using the ISR, double wall ring, SDR, and MIR, a wide range of sensitivity in surface forces (fN to nN) can be explored as each experimental method has different sensitivities. Measurements will be compared to foam stability.

  4. Interfacial gauge methods for incompressible fluid dynamics.

    PubMed

    Saye, Robert

    2016-06-01

    Designing numerical methods for incompressible fluid flow involving moving interfaces, for example, in the computational modeling of bubble dynamics, swimming organisms, or surface waves, presents challenges due to the coupling of interfacial forces with incompressibility constraints. A class of methods, denoted interfacial gauge methods, is introduced for computing solutions to the corresponding incompressible Navier-Stokes equations. These methods use a type of "gauge freedom" to reduce the numerical coupling between fluid velocity, pressure, and interface position, allowing high-order accurate numerical methods to be developed more easily. Making use of an implicit mesh discontinuous Galerkin framework, developed in tandem with this work, high-order results are demonstrated, including surface tension dynamics in which fluid velocity, pressure, and interface geometry are computed with fourth-order spatial accuracy in the maximum norm. Applications are demonstrated with two-phase fluid flow displaying fine-scaled capillary wave dynamics, rigid body fluid-structure interaction, and a fluid-jet free surface flow problem exhibiting vortex shedding induced by a type of Plateau-Rayleigh instability. The developed methods can be generalized to other types of interfacial flow and facilitate precise computation of complex fluid interface phenomena. PMID:27386567

  5. Interfacial gauge methods for incompressible fluid dynamics

    PubMed Central

    Saye, Robert

    2016-01-01

    Designing numerical methods for incompressible fluid flow involving moving interfaces, for example, in the computational modeling of bubble dynamics, swimming organisms, or surface waves, presents challenges due to the coupling of interfacial forces with incompressibility constraints. A class of methods, denoted interfacial gauge methods, is introduced for computing solutions to the corresponding incompressible Navier-Stokes equations. These methods use a type of “gauge freedom” to reduce the numerical coupling between fluid velocity, pressure, and interface position, allowing high-order accurate numerical methods to be developed more easily. Making use of an implicit mesh discontinuous Galerkin framework, developed in tandem with this work, high-order results are demonstrated, including surface tension dynamics in which fluid velocity, pressure, and interface geometry are computed with fourth-order spatial accuracy in the maximum norm. Applications are demonstrated with two-phase fluid flow displaying fine-scaled capillary wave dynamics, rigid body fluid-structure interaction, and a fluid-jet free surface flow problem exhibiting vortex shedding induced by a type of Plateau-Rayleigh instability. The developed methods can be generalized to other types of interfacial flow and facilitate precise computation of complex fluid interface phenomena. PMID:27386567

  6. Interfacial Studies of Sized Carbon Fiber

    NASA Astrophysics Data System (ADS)

    Shahrul, S. N.; Hartini, M. N.; Hilmi, E. A.; Nizam, A.

    2010-03-01

    This study was performed to investigate the influence of sizing treatment on carbon fiber in respect of interfacial adhesion in composite materials, Epolam® 2025. Fortafil unsized carbon fiber was used to performed the experiment. The fiber was commercially surface treated and it was a polyacrylonitrile based carbon fiber with 3000 filament per strand. Epicure® 3370 was used as basic sizing chemical and dissolved in two types of solvent, ethanol and acetone for the comparison purpose. The single pull out test has been used to determine the influence of sizing on carbon fiber. The morphology of carbon fiber was observed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The apparent interfacial strength IFSS values determined by pull out test for the Epicure® 3370/ethanol sized carbon fiber pointed to a good interfacial behaviour compared to the Epicure® 3370/acetone sized carbon fiber. The Epicure® 3370/ethanol sizing agent was found to be effective in promoting adhesion because of the chemical reactions between the sizing and Epolam® 2025 during the curing process. From this work, it showed that sized carbon fiber using Epicure® 3370 with addition of ethanol give higher mechanical properties of carbon fiber in terms of shear strength and also provided a good adhesion between fiber and matrix compared to the sizing chemical that contain acetone as a solvent.

  7. Large-scale simulations of layered double hydroxide nanocomposite materials

    NASA Astrophysics Data System (ADS)

    Thyveetil, Mary-Ann

    Layered double hydroxides (LDHs) have the ability to intercalate a multitude of anionic species. Atomistic simulation techniques such as molecular dynamics have provided considerable insight into the behaviour of these materials. We review these techniques and recent algorithmic advances which considerably improve the performance of MD applications. In particular, we discuss how the advent of high performance computing and computational grids has allowed us to explore large scale models with considerable ease. Our simulations have been heavily reliant on computational resources on the UK's NGS (National Grid Service), the US TeraGrid and the Distributed European Infrastructure for Supercomputing Applications (DEISA). In order to utilise computational grids we rely on grid middleware to launch, computationally steer and visualise our simulations. We have integrated the RealityGrid steering library into the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) 1 . which has enabled us to perform re mote computational steering and visualisation of molecular dynamics simulations on grid infrastruc tures. We also use the Application Hosting Environment (AHE) 2 in order to launch simulations on remote supercomputing resources and we show that data transfer rates between local clusters and super- computing resources can be considerably enhanced by using optically switched networks. We perform large scale molecular dynamics simulations of MgiAl-LDHs intercalated with either chloride ions or a mixture of DNA and chloride ions. The systems exhibit undulatory modes, which are suppressed in smaller scale simulations, caused by the collective thermal motion of atoms in the LDH layers. Thermal undulations provide elastic properties of the system including the bending modulus, Young's moduli and Poisson's ratios. To explore the interaction between LDHs and DNA. we use molecular dynamics techniques to per form simulations of double stranded, linear and plasmid DNA up

  8. Quaternized graphene oxide nanocomposites as fast hydroxide conductors.

    PubMed

    Zarrin, Hadis; Fu, Jing; Jiang, Gaopeng; Yoo, Skylar; Lenos, Jared; Fowler, Michael; Chen, Zhongwei

    2015-02-24

    Nanocomposites play a key role in performance improvements of hydroxide conductors employed in a wide range of alkaline-electrochemical systems such as fuel cells and metal-air batteries. Graphene oxide (GO) nanosheets are considered to be outstanding nanofillers for polymeric nanocomposites on account of their excellent physicochemical strength and electrochemical properties. In this work, a fast hydroxide conductor was developed on the basis of a chemically modified GO nanocomposite membrane. The high surface area of GO was functionalized with highly stable hydroxide-conductive groups using a dimethyloctadecyl [3-(trimethoxysilyl)propyl]ammonium chloride (DMAOP) precursor, named QAFGO, and then composed with porous polybenzimidazole PBI (pPBI) as a well-suited polymeric backbone. The nanocomposite exhibited outstanding hydroxide conductivity of 0.085 S cm(-1), high physicochemical strength, and electrochemical stability for 21 days. An alkaline fuel cell (AFC) setup was fabricated to determine the functionality of QAFGO/pPBI nanocomposite in an alkaline-based system. The high AFC performance with peak power density of 86.68 mW cm(-2) demonstrated that QAFGO/pPBI nanocomposite membrane has promising potential to be employed as a reliable hydroxide conductor for electrochemical systems working in alkaline conditions. PMID:25644712

  9. [Transient UV absorption spectra of artemisinin reacting with sodium hydroxide].

    PubMed

    Gao, Yan-Jun; Ping, Li; Yang, Li-Jun; Wang, Qi-Ming; Xue, Jun-Peng; Wu, Da-Cheng; Li, Rui-Xia

    2009-03-01

    UV absorption spectrum of artemisinin and transient absorption spectra of various concentrations of artemisinin reacting with sodium hydroxide were measured by using an intensified spectroscopic detector ICCD. The exposure time of each spectrum was 0.1 ms. Results indicate that artemisinin has an obvious UV absorption band centered at 212.52 nm and can react with sodium hydroxide easily. All absorption spectra of different concentrations of artemisinin reacting with sodium hydroxide have the similar changes, but the moment at which the changes happened is different. After adding sodium hydroxide into artemisinin in ethanol solution, there was a new absorption band centered at 288 nm appearing firstly. As reaction went on, the intensity of another absorption band centered at 260 nm increased gradually. At the end of the reaction, a continuous absorption band from 200 to 350 nm with the peak at 245 nm formed finally. No other transient absorption spectral data are available on the reaction of artemisinin with sodium hydroxide currently. The new spectral information obtained in this experiment provides very important experimental basis for understanding the properties of artemisinin reacting with alkaline medium and is useful for correctly using of artemisinin as a potential anticancer drug.

  10. Biocompatibility of Intracanal Medications Based on Calcium Hydroxide

    PubMed Central

    Andolfatto, Carolina; da Silva, Guilherme Ferreira; Cornélio, Ana Livia Gomes; Guerreiro-Tanomaru, Juliane Maria; Tanomaru-Filho, Mario; Faria, Gisele; Bonetti-Filho, Idomeo; Cerri, Paulo Sérgio

    2012-01-01

    Objective. The aim of this study was to evaluate the rat subcutaneous tissue reaction to calcium hydroxide-based intracanal medicaments, UltraCal XS (calcium hydroxide, barium sulphate, aqueous matrix), Hydropast (calcium hydroxide, barium sulphate, and propyleneglycol), and Calen (Calcium hydroxide, zinc oxide, colophony, and polyethyleneglycol), used as a control. Methods. Forty-eight rats (Rattus Norvegicus Holtzman) were distributed in three groups: Calen, UltraCal XS, and Hydropast. Polyethylene tubes filled with one of the medicaments were implanted in the dorsal subcutaneous. After 7 and 30 days, the implants were removed and the specimens were fixed and embedded in paraffin. Morphological and quantitative analyses were carried out in the HE-stained sections. The numerical density of inflammatory cells in the capsule was evaluated and statistical analyses were performed (P ≤ 0.05). Results. At 7 days, all materials induced an inflammatory reaction in the subcutaneous tissue adjacent to the implants. In all groups, a significant reduction in the number of inflammatory cells and giant cells was verified in the period of 30 days. Conclusion. These results indicate that the calcium hydroxide-based medicaments evaluated present biocompatibility similar to Calen. PMID:23320187

  11. Arsenate removal by layered double hydroxides embedded into spherical polymer beads: Batch and column studies.

    PubMed

    Nhat Ha, Ho Nguyen; Kim Phuong, Nguyen Thi; Boi An, Tran; Mai Tho, Nguyen Thi; Ngoc Thang, Tran; Quang Minh, Bui; Van Du, Cao

    2016-01-01

    In this study, the performance of poly(layered double hydroxides) [poly(LDHs)] beads as an adsorbent for arsenate removal from aqueous solution was investigated. The poly(LDHs) beads were prepared by immobilizing LDHs into spherical alginate/polyvinyl alcohol (PVA)-glutaraldehyde beads (spherical polymer beads). Batch adsorption studies were conducted to assess the effect of contact time, solution pH, initial arsenate concentrations and co-existing anions on arsenate removal performance. The potential reuse of these poly(LDHs) beads was also investigated. Approximately 79.1 to 91.2% of arsenic was removed from an arsenate solution (50 mg As L(-1)) by poly(LDHs). The adsorption data were well described by the pseudo-second-order kinetics model and the Langmuir isotherm model, and the adsorption capacities of these poly(LDHs) beads at pH 8 were from 1.64 to 1.73 mg As g(-1), as calculated from the Langmuir adsorption isotherm. The adsorption ability of the poly(LDHs) beads decreased by approximately 5-6% after 5 adsorption-desorption cycles. Phosphates markedly decreased arsenate removal. The effect of co-existing anions on the adsorption capacity declined in the following order: HPO4 (2-) > HCO3 (-) > SO4 (2-) > Cl(-). A fixed-bed column study was conducted with real-life arsenic-containing water. The breakthrough time was found to be from 7 to 10 h. Under optimized conditions, the poly(LDHs) removed more than 82% of total arsenic. The results obtained in this study will be useful for further extending the adsorbents to the field scale or for designing pilot plants in future studies. From the viewpoint of environmental friendliness, the poly(LDHs) beads are a potential cost-effective adsorbent for arsenate removal in water treatment. PMID:26818806

  12. Arsenate removal by layered double hydroxides embedded into spherical polymer beads: Batch and column studies.

    PubMed

    Nhat Ha, Ho Nguyen; Kim Phuong, Nguyen Thi; Boi An, Tran; Mai Tho, Nguyen Thi; Ngoc Thang, Tran; Quang Minh, Bui; Van Du, Cao

    2016-01-01

    In this study, the performance of poly(layered double hydroxides) [poly(LDHs)] beads as an adsorbent for arsenate removal from aqueous solution was investigated. The poly(LDHs) beads were prepared by immobilizing LDHs into spherical alginate/polyvinyl alcohol (PVA)-glutaraldehyde beads (spherical polymer beads). Batch adsorption studies were conducted to assess the effect of contact time, solution pH, initial arsenate concentrations and co-existing anions on arsenate removal performance. The potential reuse of these poly(LDHs) beads was also investigated. Approximately 79.1 to 91.2% of arsenic was removed from an arsenate solution (50 mg As L(-1)) by poly(LDHs). The adsorption data were well described by the pseudo-second-order kinetics model and the Langmuir isotherm model, and the adsorption capacities of these poly(LDHs) beads at pH 8 were from 1.64 to 1.73 mg As g(-1), as calculated from the Langmuir adsorption isotherm. The adsorption ability of the poly(LDHs) beads decreased by approximately 5-6% after 5 adsorption-desorption cycles. Phosphates markedly decreased arsenate removal. The effect of co-existing anions on the adsorption capacity declined in the following order: HPO4 (2-) > HCO3 (-) > SO4 (2-) > Cl(-). A fixed-bed column study was conducted with real-life arsenic-containing water. The breakthrough time was found to be from 7 to 10 h. Under optimized conditions, the poly(LDHs) removed more than 82% of total arsenic. The results obtained in this study will be useful for further extending the adsorbents to the field scale or for designing pilot plants in future studies. From the viewpoint of environmental friendliness, the poly(LDHs) beads are a potential cost-effective adsorbent for arsenate removal in water treatment.

  13. Synthesis of protocatechuic acid–zinc/aluminium–layered double hydroxide nanocomposite as an anticancer nanodelivery system

    SciTech Connect

    Barahuie, Farahnaz; Hussein, Mohd Zobir; Gani, Shafinaz Abd; Fakurazi, Sharida; Zainal, Zulkarnain

    2015-01-15

    Protocatechuic acid, an active anticancer agent, has been intercalated into Zn/Al–layered double hydroxide at Zn/Al=2) using two different preparation methods, co-precipitation and ion-exchange, which are labelled as PZAE and PZAC, respectively. The release of protocatechuate from the nanocomposites occurred in a controlled manner and was fitted satisfactorily to pseudo-second order kinetics. The basal spacing of the resulting nanocomposites PZAE and PZAC was 10.2 and 11.0 Å, respectively, indicating successful intercalation of protocatechuate anions into the interlayer galleries of Zn/Al–NO{sub 3}–LDH in a monolayer arrangement with angles of 24 and 33° from the z-axis in PZAE and PZAC, respectively. The formation of nanocomposites was further confirmed by a Fourier transform infrared study. Thermogravimetric and differential thermogravimetric analyses indicated that the thermal stability of the intercalated protocatechuic acid was significantly enhanced compared to its free protocatechuic acid, and the drug content in the nanocomposites was estimated to be approximately 32.6% in PZAE and 29.2% in PZAC. Both PZAE and PZAC nanocomposites inhibit the growth of human cervical, liver and colorectal cancer cell lines and exhibit no toxic effects towards normal fibroblast 3T3 cell after 72 h of treatment. - Graphical abstract: Protocatechuate anions were arranged in monolayer mode with the angle of 24° for PZAE and 33° for PZAC from Z axis to maximize interaction between carboxylate groups and brucite-like layers. - Highlights: • Two methods gave nanocomposites with slightly different physico-chemical properties. • PZAE and PZAC have the potential to be used as a controlled release formulation. • The thermal stability of PA is markedly enhanced upon the intercalation process. • Higher cancer cell growth inhibition for PZAE and PZAC nanocomposites than for PA.

  14. Di- versus Trinuclear Copper(II) Cryptate for the Uptake of Dicarboxylate Anions.

    PubMed

    Esteves, Catarina V; Mateus, Pedro; André, Vânia; Bandeira, Nuno A G; Calhorda, Maria José; Ferreira, Liliana P; Delgado, Rita

    2016-07-18

    Searching for receptors selective for the binding of dicarboxylate anions, the copper(II) complexes of the known ditopic octaazacryptand (t2pN8), derived from bistren [tren = tris(2-aminoethyl)amine] linked by p-xylyl spacers, were re-examined, with the expectation of observing a selective binding of oxalate or malonate by bridging the two copper centers of the [Cu2(t2pN8)(H2O)2](4+) receptor. Solution studies involving the supramolecular species formed by the receptor and oxalate (oxa(2-)), malonate (mal(2-)), and succinate (suc(2-)) anions are reported. The determined association constants revealed the unexpected formation of a 3:1:1 Cu/t2pN8/anion stoichiometry for the cascade species with oxa(2-) and mal(2-), and the single crystal X-ray structural characterization confirmed the presence of tricopper(II) complexes, with an unusual binding mode for the dicarboxylate anions. Each of the two copper atoms binds four nitrogen donor atoms of the t2pN8 cryptand and one additional hydroxide group, which bridges to the third copper. The square planar environment of this one is complete with two oxygen atoms from the oxalate (or the malonate). The two copper centers bound to the tren heads are ∼6.5 Å apart, each one at about 3.5 Å from the third Cu center. These studies were complemented by SQUID magnetization measurements and DFT calculations. The magnetic susceptibility measurements of the oxalate cascade complex showed a strong magnetic coupling (J = - 210 cm(-1)) between the Cu centers at a short distance (3.5 Å), while the coupling between the two equivalent Cu atoms (∼6.5 Å) was only -70 cm(-1). This result was well reproduced by DFT calculations. PMID:27355987

  15. Intercalation chemistry in a LDH system: anion exchange process and staging phenomenon investigated by means of time-resolved, in situ X-ray diffraction.

    PubMed

    Taviot-Guého, Christine; Feng, Yongjun; Faour, Azzam; Leroux, Fabrice

    2010-07-14

    Using time-resolved, in situ energy-dispersive X-ray diffraction (EDXRD), the formation of interstratified LDH structures, with alternate interlayer spaces occupied by different anions, have been demonstrated during anion exchange reactions. Novel hybrid LDH nanostructures can thus be prepared, combining the physicochemical properties of two intercalated anions plus those of the LDH host. A general trend is that inorganic-inorganic anion exchange reactions occur in a one-step process while inorganic-organic exchanges may proceed via a second-stage intermediate, suggesting that staging occurs partly as a result of organic-inorganic separation. Yet, other influencing parameters must be considered such as LDH host composition, LDH affinity for different anions and LDH particle size as well as extrinsic parameters like the reaction temperature. Hence, a correlation between the occurrence of staging phenomenon and the difficulty of the exchange of the initial anion is observed, suggesting that staging is needed to overcome the energy barrier in the case of the exchange by organic anions. Notwithstanding the LiAl(2) system, staging has mainly been observed with Zn(2)Cr LDH host so far, a peculiar LDH composition with a unique Zn/Cr ratio of two and a local order of the cations within the hydroxide layers. The formation of a higher order-staged intermediate than stage two, observed during the exchange reaction of CO(3)(2-) or SO(4)(2-) anions with Zn(2)Cr-tartrate, is in favour of a Daumas-Herold model although this model implies a bending of LDH layers. The analysis of the X-ray powder diffraction pattern of Zn(2)Cr-Cl/tartrate second-stage intermediate, isolated almost as a pure phase during the exchange of Cl(-) with tartrate anions in Zn(2)Cr LDH, indicates a disorder in the stacking sequence and a relative proportion of the two kinds of interlayers slightly different from 50/50. Besides, the microstructural analysis of the XRD pattern reveals a great reduction of the

  16. Equilibrium and kinetics studies on As(V) and Sb(V) removal by Fe2+ -doped Mg-Al layered double hydroxides.

    PubMed

    Kameda, Tomohito; Kondo, Eisuke; Yoshioka, Toshiaki

    2015-03-15

    Mg-Al layered double hydroxides (Mg-Al LDHs) doped with Fe(2+) adsorbed As(V) [Formula: see text] and Sb(V) [Formula: see text] from an aqueous solution through anion exchange with Cl(-) intercalated in the LDH interlayer. Fe(2+)-doped Mg-Al LDH exhibited superior As(V) removal compared with Mg-Al LDH. The oxidation of Fe(2+) doped in the Mg-Al LDH host layer to Fe(3+) increased the positive layer charge of the LDH, thus increasing the anion-uptake capacity owing to stronger electrostatic attractive force between the positively charged layer and the anion. However, Fe(2+)-doped Mg-Al LDH was not superior to Mg-Al LDH in terms of Sb(V) removal. This was attributed to the preferential intercalation of OH(-) over [Formula: see text] . The As(V) and Sb(V) removal by LDH followed Langmuir-type adsorption, which proceeded via a pseudo-first-order reaction. The equilibrium and kinetics studies confirm that the adsorption of As(V) and Sb(V) by Fe(2+)-doped Mg-Al LDH was the result of chemical adsorption, involving the anion exchange of [Formula: see text] and [Formula: see text] with the intercalated Cl(-).

  17. Reflectance spectroscopy of low atomic weight and Na-rich minerals: Borates, hydroxides, nitrates, nitrites, and peroxides

    NASA Astrophysics Data System (ADS)

    Cloutis, E.; Berg, B.; Mann, P.; Applin, D.

    2016-01-01

    We have measured reflectance spectra (0.35-20 μm) of a suite of minerals and synthetic compounds that contain low-Z (⩽Na) elements as the major cation and/or the major anion in oxides/oxyhydroxides, and are relevant to planetary geology and astrobiology. The suite comprises Na-borates, Na-, K-, Ca-hydroxides, nitrates, nitrites, and peroxides. Na-borate spectra exhibit B-O fundamental vibrations between 7 and 14 μm, and overtones/combinations of these bands in the 1.55, 1.75, 2.15, and 2.25 μm regions. Na-, K-, and Ca-hydroxide reflectance spectra are characterized by OH and metal-OH fundamental vibrations near 3, 8, and 18 μm, and a number of overtone and combination absorption bands at shorter wavelengths, and a characteristic metal-OH band near 2.35 μm. The nitrate and nitrite spectra exhibit fundamental N-O vibrations in the 7-14 μm region and numerous combinations and overtones that are still detectable to as low as ∼1.8 μm. Na-peroxide is largely spectrally featureless below 24 μm, making its detection problematic, while H-peroxide has many OH-related absorption features below 2.5 μm that differ in position from those of H2O ice and liquid. The results of this study indicate that the borates, hydroxides, nitrates, nitrite, and hydrogen peroxide can all be uniquely identified using characteristic absorption features that are present below 2.5 μm. However, some of these features are weak, and their detectability will depend on the types and abundances of any accessory phases that may be present.

  18. Interfacial fracture between highly crosslinked polymer networks and a solid surface: Effect of interfacial bond density

    SciTech Connect

    STEVENS,MARK J.

    2000-03-23

    For highly crosslinked, polymer networks bonded to a solid surface, the effect of interfacial bond density as well as system size on interfacial fracture is studied molecular dynamics simulations. The correspondence between the stress-strain curve and the sequence of molecular deformations is obtained. The failure strain for a fully bonded surface is equal to the strain necessary to make taut the average minimal path through the network from the bottom solid surface to the top surface. At bond coverages less than full, nanometer scale cavities form at the surface yielding an inhomogeneous strain profile. The failure strain and stress are linearly proportional to the number of bonds at the interface unless the number of bonds is so few that van der Waals interactions dominate. The failure is always interfacial due to fewer bonds at the interface than in the bulk.

  19. Phosphate removal from water by a novel zeolite/lanthanum hydroxide hybrid material prepared from coal fly ash.

    PubMed

    Xie, Jie; Lai, Li; Lin, Lidan; Wu, Deyi; Zhang, Zhenjia; Kong, Hainan

    2015-01-01

    This study was undertaken to investigate the effectiveness of the hybrid adsorbent, which was synthesized from coal fly ash and was composed of lanthanum hydroxide and zeolite (La-ZFA), for phosphate removal from water. Long-term repeated adsorption tests for 30 days showed that the maximum removal capacity of the material reached 66.09 mg P/g. The fractionation of adsorbed phosphorus indicated that phosphate immobilized by La-ZFA was quite irreversible and was dominated by HCl-P fraction. It was suggested that the immobilization of phosphate was mainly attributed to lanthanum hydroxide and was slightly influenced by coexistence of other anions (Cl(-), NO3(-), SO4(2-), and HCO3(-)). At a La/P molar ratio between 1.5:1 and 2.0:1, a nearly complete removal (above 98%) of phosphate could be achieved. La-ZFA also exhibited great performance for removing phosphate from lake water (97.29%) as well as the effluent from wastewater treatment plant (97.86%), respectively. In addition, based on the results of the present study, it was believed that La-ZFA could be a potential material for phosphate removal in practical application.

  20. Phosphate removal from water by a novel zeolite/lanthanum hydroxide hybrid material prepared from coal fly ash.

    PubMed

    Xie, Jie; Lai, Li; Lin, Lidan; Wu, Deyi; Zhang, Zhenjia; Kong, Hainan

    2015-01-01

    This study was undertaken to investigate the effectiveness of the hybrid adsorbent, which was synthesized from coal fly ash and was composed of lanthanum hydroxide and zeolite (La-ZFA), for phosphate removal from water. Long-term repeated adsorption tests for 30 days showed that the maximum removal capacity of the material reached 66.09 mg P/g. The fractionation of adsorbed phosphorus indicated that phosphate immobilized by La-ZFA was quite irreversible and was dominated by HCl-P fraction. It was suggested that the immobilization of phosphate was mainly attributed to lanthanum hydroxide and was slightly influenced by coexistence of other anions (Cl(-), NO3(-), SO4(2-), and HCO3(-)). At a La/P molar ratio between 1.5:1 and 2.0:1, a nearly complete removal (above 98%) of phosphate could be achieved. La-ZFA also exhibited great performance for removing phosphate from lake water (97.29%) as well as the effluent from wastewater treatment plant (97.86%), respectively. In addition, based on the results of the present study, it was believed that La-ZFA could be a potential material for phosphate removal in practical application. PMID:26301857

  1. Mesoporous platinum electrodes for amperometric determination of sugars with anion exchange chromatography.

    PubMed

    Han, Jee Hoon; Choi, Han Nim; Park, Sejin; Chung, Taek Dong; Lee, Won-Yong

    2010-01-01

    A simple amperometric detection (AD) method based on mesoporous platinum (Pt) electrodes has been developed for the determination of sugars (glucose, fructose, and sucrose) with high-performance anion-exchange chromatography (HPAEC). The amperometric detection is based on the direct oxidation of sugars on mesoporous Pt films formed on a gold electrode. The mesoporous Pt electrode (roughness factor of 243) sensitively responded to glucose, fructose, and sucrose in 80 mM sodium hydroxide solution as an alkaline mobile-phase for HPAEC. Under the optimum conditions, the limits of detection (S/N = 3) in these sugars were 0.24, 0.29, and 1.8 mM, for glucose, fructose, and sucrose, respectively. The reproducibility (relative standard deviation) of the measurements was less than 3.5%. The present method was applied to the determination of sugars in apple juice. The recoveries for all sugars ranged from 97 to 99%.

  2. Highly Sensitive and Fast Anion-Selective InN Quantum Dot Electrochemical Sensors

    NASA Astrophysics Data System (ADS)

    Hassan Alvi, Naveed ul; Rodriguez, Paul E. D. Soto; Gómez, Victor J.; Kumar, Praveen; Willander, Magnus; Nötzel, Richard

    2013-11-01

    Epitaxial InN quantum dots (QDs) are demonstrated as ion-selective electrode for potentiometric anion concentration measurements. The sensor reveals high sensitivity above 90 mV/decade for the detection of chlorine and hydroxyl ions in sodium chloride (NaCl), calcium chloride (CaCl2), and sodium hydroxide (NaOH) solutions. The response time is less than two seconds after which the signal is very stable and repeatable. The sensitivity for the InN QDs is about two times that for a reference InN thin film and the response time is about five times shorter. In pH buffer solutions the sensor reveals no clear response to cations. A model is presented for the high sensitivity, fast response, and ion selectivity based on the unique electronic properties of the InN surface together with the zero-dimensional nature of the QDs.

  3. Standard enthalpies of formation of francium hydroxide hydrates

    SciTech Connect

    Burylev, B.P.

    1995-03-01

    Available experimental data on standard enthalpies of formation of alkali metal hydroxide hydrates have been summarized. Using equations derived, the authors have calculated previously unknown enthalpies of formation of some lithium, sodium, potassium, rubidium, and cesium hydroxide hydrates. Taking into account the contribution of water to the enthalpies of formation of monohydrates, the authors have estimated the enthalpies of formation of francium hydroxide hydrates FrOH{center_dot}H{sub 2}O, FrOH{center_dot}2H{sub 2}O, and FrOH{center_dot}3H{sub 2}O (-745.8, -1085.8, and -1515.8 kJ mol{sup -1}, respectively).

  4. Transformation of zinc hydroxide chloride monohydrate to crystalline zinc oxide.

    PubMed

    Moezzi, Amir; Cortie, Michael; McDonagh, Andrew

    2016-04-25

    Thermal decomposition of layered zinc hydroxide double salts provides an interesting alternative synthesis for particles of zinc oxide. Here, we examine the sequence of changes occurring as zinc hydroxide chloride monohydrate (Zn5(OH)8Cl2·H2O) is converted to crystalline ZnO by thermal decomposition. The specific surface area of the resultant ZnO measured by BET was 1.3 m(2) g(-1). A complicating and important factor in this process is that the thermal decomposition of zinc hydroxide chloride is also accompanied by the formation of volatile zinc-containing species under certain conditions. We show that this volatile compound is anhydrous ZnCl2 and its formation is moisture dependent. Therefore, control of atmospheric moisture is an important consideration that affects the overall efficiency of ZnO production by this process. PMID:27030646

  5. Zinc hydroxide sulphate and its transformation to crystalline zinc oxide.

    PubMed

    Moezzi, Amir; Cortie, Michael B; McDonagh, Andrew M

    2013-10-28

    The thermal transformation of zinc hydroxide sulphate hydrate to zinc oxide has been examined using synchrotron X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, and surface area measurements. By collecting X-ray diffraction data in situ, we found that the dehydration of zinc hydroxide sulphate pentahydrate proceeded in discrete steps to form anhydrous zinc hydroxide sulphate. This compound then decomposed to a mixture of zinc oxide and a compound tentatively identified as Zn3(OH)2(SO4)2 at ~235 °C. At ~360 °C, the final dehydroxylation occurred with the formation of zinc oxy-sulphate, Zn3O(SO4)2, which then decomposed to ZnO at about ~800 °C. Interruption of the dehydration process can be used to synthesize the intermediate compounds.

  6. Sodium hydroxide catalyzed monodispersed high surface area silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Bhakta, Snehasis; Dixit, Chandra K.; Bist, Itti; Abdel Jalil, Karim; Suib, Steven L.; Rusling, James F.

    2016-07-01

    Understanding of the synthesis kinetics and our ability to modulate medium conditions allowed us to generate nanoparticles via an ultra-fast process. The synthesis medium is kept quite simple with tetraethyl orthosilicate (TEOS) as precursor and 50% ethanol and sodium hydroxide catalyst. Synthesis is performed under gentle conditions at 20 °C for 20 min Long synthesis time and catalyst-associated drawbacks are most crucial in silica nanoparticle synthesis. We have addressed both these bottlenecks by replacing the conventional Stober catalyst, ammonium hydroxide, with sodium hydroxide. We have reduced the overall synthesis time from 20 to 1/3 h, ∼60-fold decrease, and obtained highly monodispersed nanoparticles with 5-fold higher surface area than Stober particles. We have demonstrated that the developed NPs with ∼3-fold higher silane can be used as efficient probes for biosensor applications.

  7. Structure and properties of porous ceramics obtained from aluminum hydroxide

    NASA Astrophysics Data System (ADS)

    Levkov, R.; Kulkov, S.

    2016-08-01

    In this paper the study of porous ceramics obtained from aluminum hydroxide with gibbsite modification is presented. The dependence of porosity and mechanical characteristics of the material sintered at different temperatures was studied. It was shown that compressive strength of alumina ceramics increases by 40 times with decreasing the pore volume from 65 to 15%. It was shown that aluminum hydroxide may be used for pore formation and pore volume in the sintered ceramics can be controlled by varying the aluminum hydroxide concentration and sintering temperature. Based on these results one can conclude that the obtained structure is very close to inorganic bone matrix and can be used as promising material for bone implants production.

  8. Suppressing the dendritic growth of zinc in an ionic liquid containing cationic and anionic zinc complexes for battery applications.

    PubMed

    Liu, Zhen; Pulletikurthi, Giridhar; Lahiri, Abhishek; Cui, Tong; Endres, Frank

    2016-05-10

    Metallic zinc is a promising negative electrode for high energy rechargeable batteries due to its abundance, low-cost and non-toxic nature. However, the formation of dendritic zinc and low Columbic efficiency in aqueous alkaline solutions during charge/discharge processes remain a great challenge. Here we demonstrate that the dendritic growth of zinc can be effectively suppressed in an ionic liquid electrolyte containing highly concentrated cationic and anionic zinc complexes obtained by dissolving zinc oxide and zinc trifluoromethylsulfonate in a protic ionic liquid, 1-ethylimidazolium trifluoromethylsulfonate. The presence of both cationic and anionic zinc complexes alters the interfacial structure at the electrode/electrolyte interface and influences the nucleation and growth of zinc, leading to compact, homogeneous and dendrite-free zinc coatings. This study also provides insights into the development of highly concentrated metal salts in ionic liquids as electrolytes to deposit dendrite-free zinc as an anode material for energy storage applications. PMID:27080261

  9. Effect of oxide formation mechanisms on lead adsorption by biogenic manganese (hydr)oxides, iron (hydr)oxides, and their mixtures.

    PubMed

    Nelson, Yarrow M; Lion, Leonard W; Shuler, Michael L; Ghiorse, William C

    2002-02-01

    The effects of iron and manganese (hydr)oxide formation processes on the trace metal adsorption properties of these metal (hydr)oxides and their mixtures was investigated by measuring lead adsorption by iron and manganese (hydr)oxides prepared by a variety of methods. Amorphous iron (hydr)oxide formed by fast precipitation at pH 7.5 exhibited greater Pb adsorption (gamma(max) = 50 mmol of Pb/mol of Fe at pH 6.0) than iron (hydr)oxide formed by slow, diffusion-controlled oxidation of Fe(II) at pH 4.5-7.0 or goethite. Biogenic manganese(III/IV) (hydr)oxide prepared by enzymatic oxidation of Mn(II) by the bacterium Leptothrix discophora SS-1 adsorbed five times more Pb (per mole of Mn) than an abiotic manganese (hydr)oxide prepared by oxidation of Mn(II) with permanganate, and 500-5000 times more Pb than pyrolusite oxides (betaMnO2). X-ray crystallography indicated that biogenic manganese (hydr)oxide and iron (hydr)oxide were predominantly amorphous or poorly crystalline and their X-ray diffraction patterns were not significantly affected by the presence of the other (hydr)oxide during formation. When iron and manganese (hydr)oxides were mixed after formation, or for Mn biologically oxidized with iron(III) (hydr)oxide present, observed Pb adsorption was similar to that expected for the mixture based on Langmuir parameters for the individual (hydr)oxides. These results indicate that interactions in iron/manganese (hydr)oxide mixtures related to the formation process and sequence of formation such as site masking, alterations in specific surface area, or changes in crystalline structure either did not occur or had a negligible effect on Pb adsorption by the mixtures. PMID:11871557

  10. Effect of oxide formation mechanisms on lead adsorption by biogenic manganese (hydr)oxides, iron (hydr)oxides, and their mixtures.

    PubMed

    Nelson, Yarrow M; Lion, Leonard W; Shuler, Michael L; Ghiorse, William C

    2002-02-01

    The effects of iron and manganese (hydr)oxide formation processes on the trace metal adsorption properties of these metal (hydr)oxides and their mixtures was investigated by measuring lead adsorption by iron and manganese (hydr)oxides prepared by a variety of methods. Amorphous iron (hydr)oxide formed by fast precipitation at pH 7.5 exhibited greater Pb adsorption (gamma(max) = 50 mmol of Pb/mol of Fe at pH 6.0) than iron (hydr)oxide formed by slow, diffusion-controlled oxidation of Fe(II) at pH 4.5-7.0 or goethite. Biogenic manganese(III/IV) (hydr)oxide prepared by enzymatic oxidation of Mn(II) by the bacterium Leptothrix discophora SS-1 adsorbed five times more Pb (per mole of Mn) than an abiotic manganese (hydr)oxide prepared by oxidation of Mn(II) with permanganate, and 500-5000 times more Pb than pyrolusite oxides (betaMnO2). X-ray crystallography indicated that biogenic manganese (hydr)oxide and iron (hydr)oxide were predominantly amorphous or poorly crystalline and their X-ray diffraction patterns were not significantly affected by the presence of the other (hydr)oxide during formation. When iron and manganese (hydr)oxides were mixed after formation, or for Mn biologically oxidized with iron(III) (hydr)oxide present, observed Pb adsorption was similar to that expected for the mixture based on Langmuir parameters for the individual (hydr)oxides. These results indicate that interactions in iron/manganese (hydr)oxide mixtures related to the formation process and sequence of formation such as site masking, alterations in specific surface area, or changes in crystalline structure either did not occur or had a negligible effect on Pb adsorption by the mixtures.

  11. Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review.

    PubMed

    He, Jie; Yang, Xiaofang; Men, Bin; Wang, Dongsheng

    2016-01-01

    The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals (OH) from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH. Hence, it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology. Due to the complex reaction system, the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating, and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies. Iron-based materials usually possess high catalytic activity, low cost, negligible toxicity and easy recovery, and are a superior type of heterogeneous Fenton catalysts. Therefore, this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials. OH, hydroperoxyl radicals/superoxide anions (HO2/O2(-)) and high-valent iron are the three main types of reactive oxygen species (ROS), with different oxidation reactivity and selectivity. Based on the mechanisms of ROS generation, the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron, the heterogeneous catalysis mechanism, and the heterogeneous reaction-induced homogeneous mechanism. Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed. Finally, related future research directions are also suggested. PMID:26899649

  12. Novel pseudo-delocalized anions for lithium battery electrolytes.

    PubMed

    Jónsson, Erlendur; Armand, Michel; Johansson, Patrik

    2012-05-01

    A novel anion concept of pseudo-delocalized anions, anions with distinct positive and negative charge regions, has been studied by a computer aided synthesis using DFT calculations. With the aim to find safer and better performing lithium salts for lithium battery electrolytes two factors have been evaluated: the cation-anion interaction strength via the dissociation reaction LiAn ⇌ Li(+) + An(-) and the anion oxidative stability via a vertical ionisation from anion to radical. Based on our computational results some of these anions have shown promise to perform well as lithium salts for modern lithium batteries and should be interesting synthetic targets for future research. PMID:22441354

  13. Click Chemistry Finds Its Way in Constructing an Ionic Highway in Anion-Exchange Membrane.

    PubMed

    Ge, Qianqian; Ran, Jin; Miao, Jibin; Yang, Zhengjin; Xu, Tongwen

    2015-12-30

    To find the way to construct an ionic highway in anion-exchange membranes (AEMs), a series of side-chain-type alkaline polymer electrolytes (APEs) based on poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) polymer backbones were synthesized via Cu(I)-catalyzed click chemistry. The resulting triazole groups and quaternary ammonium (QA) groups facilitate the formation of a continuous hydrogen bond network, which will lead to high hydroxide conductivity according to Grotthuss-type mechanism. Microphase separation induced by long alkyl side chains contributes at the same time to further improving the hydroxide conductivity of the resultant AEMs. Hydroxide conductivity as high as 52.8 mS/cm is obtained for membrane TA-14C-1.21 (IEC = 1.21 mmol/g) with the longest pendant chain at 30 °C, and the conductivity can be increased to 140 mS/cm when the temperature was increased to 80 °C. Moreover, the corresponding water uptake is only 8.6 wt % at 30 °C. In the meantime, the membrane properties can be tuned by precisely regulating the hydrophilic/hydrophobic ratio in the cationic head groups. Compared with AEMs containing triazole and quaternized trimethylammonium head groups, enhanced dimensional stability and mechanical properties are obtained by tuning side-chain chemistry. However, the alkaline stability of the membrane is not as stable as anticipated, probably because of the existence of the triazole ring. Further study will be focused on increasing the alkali stability of the membrane. We envisage that the side-chain-type APEs meditated by click chemistry bearing long hydrophobic side chains pendant to the cationic head groups hold promise as a novel AEMs material. PMID:26645427

  14. Studies of anions sorption on natural zeolites.

    PubMed

    Barczyk, K; Mozgawa, W; Król, M

    2014-12-10

    This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method.

  15. Tunable high performance cross-linked alkaline anion exchange membranes for fuel cell applications.

    PubMed

    Robertson, Nicholas J; Kostalik, Henry A; Clark, Timothy J; Mutolo, Paul F; Abruña, Héctor D; Coates, Geoffrey W

    2010-03-17

    Fuel cells are energy conversion devices that show great potential in numerous applications ranging from automobiles to portable electronics. However, further development of fuel cell components is necessary for them to become commercially viable. One component critical to their performance is the polymer electrolyte membrane, which is an ion conductive medium separating the two electrodes. While proton conducting membranes are well established (e.g., Nafion), hydroxide conducting membranes (alkaline anion exchange membranes, AAEMs) have been relatively unexplored by comparison. Operating under alkaline conditions offers significant efficiency benefits, especially for the oxygen reduction reaction; therefore, effective AAEMs could significantly advance fuel cell technologies. Here we demonstrate the use of ring-opening metathesis polymerization to generate new cross-linked membrane materials exhibiting high hydroxide ion conductivity and good mechanical properties. Cross-linking allows for increased ion incorporation, which, in turn supports high conductivities. This facile synthetic approach enables the preparation of cross-linked materials with the potential to meet the demands of hydrogen-powered fuel cells as well as direct methanol fuel cells. PMID:20178312

  16. Tunable High Performance Cross-Linked Alkaline Anion Exchange Membranes for Fuel Cell Applications

    SciTech Connect

    Robertson, Nicholas J.; Kostalik, IV, Henry A.; Clark, Timothy J.; Mutolo, Paul F.; Abruña, Héctor D.; Coates, Geoffrey W.

    2010-02-23

    Fuel cells are energy conversion devices that show great potential in numerous applications ranging from automobiles to portable electronics. However, further development of fuel cell components is necessary for them to become commercially viable. One component critical to their performance is the polymer electrolyte membrane, which is an ion conductive medium separating the two electrodes. While proton conducting membranes are well established (e.g., Nafion), hydroxide conducting membranes (alkaline anion exchange membranes, AAEMs) have been relatively unexplored by comparison. Operating under alkaline conditions offers significant efficiency benefits, especially for the oxygen reduction reaction; therefore, effective AAEMs could significantly advance fuel cell technologies. Here we demonstrate the use of ring-opening metathesis polymerization to generate new cross-linked membrane materials exhibiting high hydroxide ion conductivity and good mechanical properties. Cross-linking allows for increased ion incorporation, which, in turn supports high conductivities. This facile synthetic approach enables the preparation of cross-linked materials with the potential to meet the demands of hydrogen-powered fuel cells as well as direct methanol fuel cells.

  17. Enhanced performance of anion exchange membranes via crosslinking of ion cluster regions for fuel cells

    NASA Astrophysics Data System (ADS)

    Lai, Ao Nan; Guo, Dong; Lin, Chen Xiao; Zhang, Qiu Gen; Zhu, Ai Mei; Ye, Mei Ling; Liu, Qing Lin

    2016-09-01

    Development of anion exchange membranes (AEMs) with high hydroxide conductivity, good dimensional and alkaline stabilities is still a challenge for the practical application of AEM fuel cells. In this study, we report a new strategy to prepare high-performance AEMs with crosslinked ionic regions. A series of phenolphthalein-containing poly(arylene ether sulfone)s crosslinked AEMs was synthesized by grafting ion groups selectively and densely on the phenolphthalein units to form ion clusters that are further crosslinked to generate the hydrophilic ionic regions. The crosslinking reaction not only improved the dimensional stability of the AEMs, but also increased the aggregation of the ion clusters leading to the formation of hydrophilic/hydrophobic phase-separated morphology and ion-conducting channels. As a result, enhancements in both ion conductivity and dimensional stability can be achieved. The crosslinked AEMs showed high hydroxide conductivities in the range of 52.2-143.4 mS cm-1 from 30 to 80 °C and a superb ratio of relative conductivity to relative swelling at 80 °C. Furthermore, the crosslinked AEMs also exhibited good mechanical properties, thermal and alkaline stabilities and desirable single cell performance. This work presents a promising strategy for the synthesis of high-performance AEMs for fuel cells.

  18. Using AFM to probe the complexation of DNA with anionic lipids mediated by Ca(2+): the role of surface pressure.

    PubMed

    Luque-Caballero, Germán; Martín-Molina, Alberto; Sánchez-Treviño, Alda Yadira; Rodríguez-Valverde, Miguel A; Cabrerizo-Vílchez, Miguel A; Maldonado-Valderrama, Julia

    2014-04-28

    Complexation of DNA with lipids is currently being developed as an alternative to classical vectors based on viruses. Most of the research to date focuses on cationic lipids owing to their spontaneous complexation with DNA. Nonetheless, recent investigations have revealed that cationic lipids induce a large number of adverse effects on DNA delivery. Precisely, the lower cytotoxicity of anionic lipids accounts for their use as a promising alternative. However, the complexation of DNA with anionic lipids (mediated by cations) is still in early stages and is not yet well understood. In order to explore the molecular mechanisms underlying the complexation of anionic lipids and DNA we proposed a combined methodology based on the surface pressure-area isotherms, Gibbs elasticity and Atomic Force Microscopy (AFM). These techniques allow elucidation of the role of the surface pressure in the complexation and visualization of the interfacial aggregates for the first time. We demonstrate that the DNA complexes with negatively charged model monolayers (DPPC/DPPS 4 : 1) only in the presence of Ca(2+), but is expelled at very high surface pressures. Also, according to the Gibbs elasticity plot, the complexation of lipids and DNA implies a whole fluidisation of the monolayer and a completely different phase transition map in the presence of DNA and Ca(2+). AFM imaging allows identification for the first time of specific morphologies associated with different packing densities. At low surface coverage, a branched net like structure is observed whereas at high surface pressure fibers formed of interfacial aggregates appear. In summary, Ca(2+) mediates the interaction between DNA and negatively charged lipids and also the conformation of the ternary system depends on the surface pressure. Such observations are important new generic features of the interaction between DNA and anionic lipids. PMID:24668321

  19. Optimization of UV absorptivity of layered double hydroxide by intercalating organic UV-absorbent molecules.

    PubMed

    Mohsin, Sumaiyah Megat Nabil; Hussein, Mohd Zobir; Sarijo, Siti Halimah; Fakurazi, Sharida; Arulselvan, Palanisamy; Taufiq-Yap, Yun Hin

    2014-08-01

    Intercalation of Zn/Al layered double hydroxide (LDH) with benzophenone 9 (B9), a strong ultraviolet (UV) absorber, had been carried out by two different routes; co-precipitation and ion exchange method. Powder X-ray diffraction (PXRD) patterns of co-precipitated (ZB9C) and ion exchanged product (ZB91) showed basal spacing of 15.9 angstrom and 16.6 angstrom, respectively, as a result of the intercalation of B9 anions into the lamellae spaces of LDH. Intercalation was further confirmed by Fourier transform infrared spectra (FTIR), carbon, hydrogen, nitrogen and sulfur (CHNS) and thermogravimetric and differential thermogravimetric (TGA/DTG) studies. UV-vis absorption properties of the nanocomposite was investigated with diffuse reflectance UV-visible spectrometer and showed broader UV absorption range. Furthermore, stability of sunscreen molecules in LDH interlayer space was tested in deionized water, artificial sea water and skin pH condition to show slow deintercalation and high retention in host. Cytotoxicity study of the synthesized nanocomposites on human dermal fibroblast (HDF) cells shows no significant cytotoxicity after 24 h exposure for test concentrations up to 25 microg/mL. PMID:25016649

  20. Synthesis, spectroscopic and electrochemical performance of pasted β-nickel hydroxide electrode in alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    Shruthi, B.; Bheema Raju, V.; Madhu, B. J.

    2015-01-01

    β-Nickel hydroxide (β-Ni(OH)2) was successfully synthesized using precipitation method. The structure and property of the β-Ni(OH)2 were characterized by X-ray diffraction (XRD), Fourier Transform infra-red (FT-IR), Raman spectra and thermal gravimetric-differential thermal analysis (TG-DTA). The results of the FTIR spectroscopy and TG-DTA studies indicate that the β-Ni(OH)2 contains water molecules and anions. The microstructural and composition studies have been performed using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) analysis. A pasted-type electrode is prepared using β-Ni(OH)2 powder as the active material on a nickel sheet as a current collector. Cyclic voltammetry (CV) and Electrochemical impedance spectroscopy (EIS) studies were performed to evaluate the electrochemical performance of the β-Ni(OH)2 electrode in 6 M KOH electrolyte. CV curves showed a pair of strong redox peaks as a result of the Faradaic redox reactions of β-Ni(OH)2. The proton diffusion coefficient (D) for the present β-Ni(OH)2 electrode material is found to be 1.44 × 10-12 cm2 s-1. Further, electrochemical impedance studies confirmed that the β-Ni(OH)2 electrode reaction processes are diffusion controlled.

  1. Methotrexatum intercalated layered double hydroxides: statistical design, mechanism explore and bioassay study.

    PubMed

    Wang, Xiao-Feng; Liu, Su-Qing; Li, Shu-Ping

    2015-04-01

    A series of methotrexatum intercalated layered double hydroxide (MTX/LDH for short) hybrids have been synthesized by a mechanochemical-hydrothermal method, the statistical experiments are planned and conducted to find out the critical factor influencing the physicochemical properties. Four variables, i.e., addition of NaOH solution, grinding duration, hydrothermal temperature and time, are chosen to play as the examined factors in the orthogonal design. Furthermore, three respective levels, i.e., high, medium and low levels, are conducted in the design. The resulting hybrids are then characterized by X-ray diffraction (XRD) patterns, transmission electron microscope (TEM) graphs and Zeta potentials. XRD diffractions indicate that MTX anions have been successfully intercalated into LDH interlayers and the amount of NaOH solution can change the gallery height greatly. The information from TEM graphs and Zeta potentials state that the increase of alkali solution gives rise to regular morphology and the increase of Zeta potentials. As a result of the statistical analysis, addition of alkali solution is the major factor affecting the morphology and drug-loading capacity. At last, the mechanism of particle growth is explored emphatically, and the anticancer efficacy of some MTX/LDH hybrids is estimated by MTT assay on A549 cells as well.

  2. Potential for Layered Double Hydroxides-Based, Innovative Drug Delivery Systems

    PubMed Central

    Zhang, Kai; Xu, Zhi Ping; Lu, Ji; Tang, Zhi Yong; Zhao, Hui Jun; Good, David A.; Wei, Ming Qian

    2014-01-01

    Layered Double Hydroxides (LDHs)-based drug delivery systems have, for many years, shown great promises for the delivery of chemical therapeutics and bioactive molecules to mammalian cells in vitro and in vivo. This system offers high efficiency and drug loading density, as well as excellent protection of loaded molecules from undesired degradation. Toxicological studies have also found LDHs to be biocompatible compared with other widely used nanoparticles, such as iron oxide, silica, and single-walled carbon nanotubes. A plethora of bio-molecules have been reported to either attach to the surface of or intercalate into LDH materials through co-precipitation or anion-exchange reaction, including amino acid and peptides, ATPs, vitamins, and even polysaccharides. Recently, LDHs have been used for gene delivery of small molecular nucleic acids, such as antisense, oligonucleotides, PCR fragments, siRNA molecules or sheared genomic DNA. These nano-medicines have been applied to target cells or organs in gene therapeutic approaches. This review summarizes current progress of the development of LDHs nanoparticle drug carriers for nucleotides, anti-inflammatory, anti-cancer drugs and recent LDH application in medical research. Ground breaking studies will be highlighted and an outlook of the possible future progress proposed. It is hoped that the layered inorganic material will open up new frontier of research, leading to new nano-drugs in clinical applications. PMID:24786098

  3. Ephemeral Fe(II)/Fe(III) layered double hydroxides in hydromorphic soils: A review

    NASA Astrophysics Data System (ADS)

    Vodyanitskii, Yu. N.; Shoba, S. A.

    2015-03-01

    Ephemeral green rust is formed seasonally in some hydromorphic soils. It consists of Fe(II)/Fe(III) layered double hydroxides with different types of interlayer anions and different oxidation degrees of iron ( x). In synthetized stoichiometric green rust, x = 0.25-0.33; in soil fougerite, it may reach 0.50-0.66. The mineral stability is provided by the partial substitution of Mg2+ for Fe2+. The ephemeral properties of the green rust are manifested in the high sensitivity to the varying redox regime in hydromorphic soils. Green rust disappears during oxidation stages, which complicates its diagnostics in soils. For green rust formation, excessively moist mineral soil needs organic matter as a source of energy for the vital activity of iron-reducing bacteria. In a gleyed Cambisol France, where fougerite is formed in the winter, the index of hydrogen partial pressure rH2 is 7.0-8.2, which corresponds to highly reducing conditions; upon the development of oxidation, fougerite is transformed into lepidocrocite. In the mineral siderite horizon of peatbogs in Belarus, where green rust is formed in the summer, rH2 is 11-14, which corresponds to the lower boundary of reducing conditions ( rH2 = 10-18); magnetite is formed in these soils in the winter season upon dehydration of the soil mass.

  4. Layered double hydroxide (LDH)-coated attapulgite for phosphate removal from aqueous solution.

    PubMed

    Fang-qun, Gan; Jian-min, Zhou; Huo-yan, Wang; Hong-ting, Zhao

    2011-01-01

    In this study, a composite adsorbent, layered double hydroxide (LDH)-coated attapulgite (LDH-AP), was synthesized and characterized. Its potential application for LDH stabilizer and phosphate (P) removal from aqueous solution was evaluated using the batch mode and continuous mode in a packed bed column. The batch experiments revealed that the data of P adsorption onto LDH-AP could be well described by the Freundlich equation, and the maximum adsorption capacity was estimated to be 6.9 mg/g. The column experiments were conducted in the tap water and the results indicated that the competing anions could slightly decrease phosphate removal. The saturated column was regenerated by 0.2 mol/L of NaOH and the regenerated column was examined for its reuse in phosphate removal. The results of this study suggested that attapulgite could be used as an applicable stabilizer of LDH and LDH-AP could be potentially used as a promising filtration medium for phosphate removal. PMID:22156122

  5. Layered Double Hydroxide Minerals as Possible Prebiotic Information Storage and Transfer Compounds

    NASA Astrophysics Data System (ADS)

    Greenwell, H. Chris; Coveney, Peter V.

    2006-02-01

    One of the fundamental difficulties when considering the origin of life on Earth is the identification of an emergent system that not only replicated, but also had the capacity to undergo discrete mutation in such a way that following generations might inherit and pass on the mutation. We speculate that the layered double hydroxide (LDH) minerals are plausible candidates for a proto-RNA molecule. We describe a hypothetical LDH-like system which, when intercalated with certain anions, forms crystals with a high degree of internal order giving rise to novel information storage structures in which replication fidelity is maintained, a concept we use to propose an explanation for interstratification in terephthalate LDHs. The external surfaces of these hypothetical crystals provide active sites whose structure and chemistry is dictated by the internal information content of the LDH. Depending on the LDH polytype, the opposing external surfaces of a crystal may give rise to reactive sites that are either complementary or mirror images of each other, and so may be chiral. We also examine similarities between these proposed “proto-RNA” structures and the DNA that encodes the hereditary information in life today, concluding with a hypothetical scenario wherein these proto-RNA molecules predated the putative RNA-world.

  6. Organo-layered double hydroxides composite thin films deposited by laser techniques

    NASA Astrophysics Data System (ADS)

    Birjega, R.; Vlad, A.; Matei, A.; Dumitru, M.; Stokker-Cheregi, F.; Dinescu, M.; Zavoianu, R.; Raditoiu, V.; Corobea, M. C.

    2016-06-01

    We used laser techniques to create hydrophobic thin films of layered double hydroxides (LDHs) and organo-modified LDHs. A LDH based on Zn-Al with Zn2+/Al3+ ratio of 2.5 was used as host material, while dodecyl sulfate (DS), which is an organic surfactant, acted as guest material. Pulsed laser deposition (PLD) and matrix assisted pulsed laser evaporation (MAPLE) were employed for the growth of the films. The organic anions were intercalated in co-precipitation step. The powders were subsequently used either as materials for MAPLE, or they were pressed and used as targets for PLD. The surface topography of the thin films was investigated by atomic force microscopy (AFM), the crystallographic structure of the powders and films was checked by X-ray diffraction. FTIR spectroscopy was used to evidence DS interlayer intercalation, both for powders and the derived films. Contact angle measurements were performed in order to establish the wettability properties of the as-prepared thin films, in view of functionalization applications as hydrophobic surfaces, owing to the effect of DS intercalation.

  7. Platelets to rings: Influence of sodium dodecyl sulfate on Zn-Al layered double hydroxide morphology

    SciTech Connect

    Yilmaz, Ceren; Unal, Ugur; Yagci Acar, Havva

    2012-03-15

    In the current study, influence of sodium dodecyl sulfate (SDS) on the crystallization of Zn-Al layered double hydroxide (LDH) was investigated. Depending on the SDS concentration coral-like and for the first time ring-like morphologies were obtained in a urea-hydrolysis method. It was revealed that the surfactant level in the starting solution plays an important role in the morphology. Concentration of surfactant equal to or above the anion exchange capacity of the LDH is influential in creating different morphologies. Another important parameter was the critical micelle concentration (CMC) of the surfactant. Surfactant concentrations well above CMC value resulted in ring-like structures. The crystallization mechanism was discussed. - Graphical abstract: Dependence of ZnAl LDH Morphology on SDS concentration. Highlights: Black-Right-Pointing-Pointer In-situ intercalation of SDS in ZnAl LDH was achieved via urea hydrolysis method. Black-Right-Pointing-Pointer Morphology of ZnAl LDH intercalated with SDS depended on the SDS concentration. Black-Right-Pointing-Pointer Ring like morphology for SDS intercalated ZnAl LDH was obtained for the first time. Black-Right-Pointing-Pointer Growth mechanism was discussed. Black-Right-Pointing-Pointer Template assisted growth of ZnAl LDH was proposed.

  8. Synthesis of protocatechuic acid-zinc/aluminium-layered double hydroxide nanocomposite as an anticancer nanodelivery system

    NASA Astrophysics Data System (ADS)

    Barahuie, Farahnaz; Hussein, Mohd Zobir; Gani, Shafinaz Abd; Fakurazi, Sharida; Zainal, Zulkarnain

    2015-01-01

    Protocatechuic acid, an active anticancer agent, has been intercalated into Zn/Al-layered double hydroxide at Zn/Al=2) using two different preparation methods, co-precipitation and ion-exchange, which are labelled as PZAE and PZAC, respectively. The release of protocatechuate from the nanocomposites occurred in a controlled manner and was fitted satisfactorily to pseudo-second order kinetics. The basal spacing of the resulting nanocomposites PZAE and PZAC was 10.2 and 11.0 Å, respectively, indicating successful intercalation of protocatechuate anions into the interlayer galleries of Zn/Al-NO3-LDH in a monolayer arrangement with angles of 24 and 33° from the z-axis in PZAE and PZAC, respectively. The formation of nanocomposites was further confirmed by a Fourier transform infrared study. Thermogravimetric and differential thermogravimetric analyses indicated that the thermal stability of the intercalated protocatechuic acid was significantly enhanced compared to its free protocatechuic acid, and the drug content in the nanocomposites was estimated to be approximately 32.6% in PZAE and 29.2% in PZAC. Both PZAE and PZAC nanocomposites inhibit the growth of human cervical, liver and colorectal cancer cell lines and exhibit no toxic effects towards normal fibroblast 3T3 cell after 72 h of treatment.

  9. Potential for layered double hydroxides-based, innovative drug delivery systems.

    PubMed

    Zhang, Kai; Xu, Zhi Ping; Lu, Ji; Tang, Zhi Yong; Zhao, Hui Jun; Good, David A; Wei, Ming Qian

    2014-01-01

    Layered Double Hydroxides (LDHs)-based drug delivery systems have, for many years, shown great promises for the delivery of chemical therapeutics and bioactive molecules to mammalian cells in vitro and in vivo. This system offers high efficiency and drug loading density, as well as excellent protection of loaded molecules from undesired degradation. Toxicological studies have also found LDHs to be biocompatible compared with other widely used nanoparticles, such as iron oxide, silica, and single-walled carbon nanotubes. A plethora of bio-molecules have been reported to either attach to the surface of or intercalate into LDH materials through co-precipitation or anion-exchange reaction, including amino acid and peptides, ATPs, vitamins, and even polysaccharides. Recently, LDHs have been used for gene delivery of small molecular nucleic acids, such as antisense, oligonucleotides, PCR fragments, siRNA molecules or sheared genomic DNA. These nano-medicines have been applied to target cells or organs in gene therapeutic approaches. This review summarizes current progress of the development of LDHs nanoparticle drug carriers for nucleotides, anti-inflammatory, anti-cancer drugs and recent LDH application in medical research. Ground breaking studies will be highlighted and an outlook of the possible future progress proposed. It is hoped that the layered inorganic material will open up new frontier of research, leading to new nano-drugs in clinical applications.

  10. Intercalation of methotrexatum into layered double hydroxides via exfoliation-reassembly process

    NASA Astrophysics Data System (ADS)

    Liu, Su-Qing; Li, Shu-Ping; Li, Xiao-Dong

    2015-03-01

    In this paper, the intercalation of methotrexatum (MTX) into layered double hydroxides (LDHs) via an exfoliation-reassembly process was reported and the resulting hybrids were then characterized by X-ray diffraction (XRD) patterns, Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM) patterns etc. In the synthesis procedure, LDHs particles were firstly delaminated into well-dispersed 2D nanosheets in formamide by ultrasonic treatment at room temperature, and then the resulting LDH nanosheets were reassembled in MTX solution to form MTX intercalated LDH (MTX/LDHs) hybrids. AFM images showed that during the exfoliation process a large part of LDHs particles were delaminated into single and double brucite layers. XRD patterns and FTIR investigations manifested the successful intercalation of MTX anions into LDHs interlayers for the final samples. It was also found out that the drug-loading capacity of the hybrids increased with the concentrations of MTX solutions, while the morphology became even aggregated. At last, the cell cytotoxicity of the hybrids was estimated by MTT assays on the human lung cancer cells (A549), and the results stated that MTX/LDHs hybrids had effective suppress role on the proliferation of cancer cells.

  11. Synthesis and characterization of layered double hydroxides and their potential as nonviral gene delivery vehicles.

    PubMed

    Balcomb, Blake; Singh, Moganavelli; Singh, Sooboo

    2015-04-01

    Layered double hydroxides (LDHs) exhibit characteristic anion-exchange chemistry making them ideal carriers of negatively charged molecules like deoxyribonucleic acid (DNA). In this study, hydrotalcite (Mg-Al) and hydrotalcite-like compounds (Mg-Fe, Zn-Al, and Zn-Fe), also known as LDHs, were evaluated for their potential application as a carrier of DNA. LDHs were prepared by coprecipitation at low supersaturation and characterized by Powder X-ray diffraction (XRD), infrared (IR), Raman, and inductively coupled plasma-optical emission spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). XRD patterns showed strong and sharp diffraction peaks for the (003) and (006) planes indicating well-ordered crystalline materials. TEM images yielded irregular circular to hexagonal-shaped particles of 50-250 nm in size. Varying degrees of DNA binding was observed for all the compounds, and nuclease digestion studies revealed that the LDHs afford some degree of protection to the bound DNA. Minimal toxicity was observed in human embryonic kidney (HEK293), cervical cancer (HeLa) and hepatocellular carcinoma (HepG2) cell lines with most showing a cell viability in excess of 80 %. All LDH complexes promoted significant levels of luciferase gene expression, with the DNA:Mg-Al LDHs proving to be the most efficient in all cell lines. PMID:25969811

  12. Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

    NASA Technical Reports Server (NTRS)

    Pitsch, S.; Krishnamurthy, R.; Arrhenius, G.; Bada, J. L. (Principal Investigator)

    2000-01-01

    Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

  13. Understanding the forces that govern packing: a density functional theory and structural investigation of anion-π-anion and nonclassical C-H···anion interactions.

    PubMed

    Brooker, Sally; White, Nicholas G; Bauzá, Antonio; Deyà, Pere M; Frontera, Antonio

    2012-10-01

    The ability of Ni(II) coordinated 4-pyrrolyl-3,5-di(2-pyridyl)-1,2,4-triazole (pldpt) to establish multiple anion-π interactions is analyzed. Experimentally, such complexes were previously shown to form strong anion-π interactions, including "π-pocket" and "π-sandwiched" motifs, in the crystal lattice. In the latter, the triazole ring is "sandwiched" by two anions forming a ternary anion-π-anion assembly (π-sandwich) which, surprisingly, gave about 0.2 Å shorter anion-π distances than in binary assemblies (where only one side of the triazole participates in the anion binding), indicating the possibility of cooperativity. In depth analysis, using dispersion-corrected density functional theory (DFT, BP86-D/def2-TZVP level of theory), shows that this ternary anion-π-anion interaction is slightly less energetically favorable than the binary anion-π interactions in isolation. Hence, the sandwich interaction is not cooperative (E(coop) is positive), but, as E(coop) contributes less than 1.5% of the total interaction energy (which is dominated by the strong electrostatic attraction of the anions to the highly π-acidic Ni(II)-coordinated triazole ring), the presence of nonclassical C-H···anion hydrogen bonds can offset this, making the short anion-π sandwich interactions the most favorable solid state conformation. PMID:22974250

  14. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Bowman-James, Kristen

    2004-12-01

    This project have focuses on the basic chemical aspects of anion receptor design of functional pH independent systems, with the ultimate goal of targeting the selective binding of sulfate, as well as design of separations strategies for selective and efficient removal of targeted anions. Key findings include: (1) the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate anion from acidic, nitrate-containing aqueous media. Areas probed during the last funding period include: the design, synthesis, and physical and structural characterization of receptors and investigation of anion and dual ion pair extraction using lipophilic amide receptors for anion binding. A new collaboration has been added to the project in addition to the one with Dr. Bruce Moyer at Oak Ridge National Laboratory, with Professor Jonathan Sessler at the University of Texas at Austin.

  15. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-12-11

    This project involves the design and synthesis of receptors for oxoanions of environmental importance, including emphasis on high level and low activity waste. Target anions have included primarily oxoanions and a study of the basic concepts behind selective binding of target anions. A primary target has been sulfate because of its deleterious influence on the vitrification of tank wastes

  16. MgAl- Layered Double Hydroxide Nanoparticles for controlled release of Salicylate.

    PubMed

    Mondal, Soumini; Dasgupta, Sudip; Maji, Kanchan

    2016-11-01

    Layered double hydroxides (LDHs), have been known for many decades as catalyst and ceramic precursors, traps for anionic pollutants, and additives for polymers. Recently, their successful synthesis on the nanometer scale opened up a whole new field for their application in nanomedicine. Here we report the efficacy of Mg1-xAlx (NO3)x (OH)2 LDH nanoparticles as a carrier and for controlled release of one of the non-steroidal anti-inflammatory drugs (NSAID), sodium salicylate. Mg1-xAlx (NO3)x (OH)2.nH2O nanoparticles were synthesized using co-precipitation method from an aqueous solution of Mg(NO3)2.6H2O and Al(NO3)3.9H2O. Salicylate was intercalated in the interlayer space of Mg-Al LDH after suspending nanoparticles in 0.0025(M) HNO3 and 0.75 (M) NaNO3 solution and using anion exchange method under N2 atmosphere. The shift in the basal planes like (003) and (006) to lower 2θ value in the XRD plot of intercalated sample confirmed the increase in basal spacing in LDH because of intercalation of salicylate into the interlayer space of LDH. FTIR spectroscopy of SA-LDH nano hybrid revealed a red shift in the frequency band of carboxylate group in salicylate indicating an electrostatic interaction between cationic LDH sheet and anionic drug. Differential thermal analysis of LDH-SA nanohybrid indicated higher thermal stability of salicylate in the intercalated form into LDH as compared to its free state. DLS studies showed a particle size distribution between 30-60 nm for pristine LDH whereas salicylate intercalated LDH exhibited a particle size distribution between 40-80nm which is ideal for its efficacy as a superior carrier for drugs and biomolecules. The cumulative release kinetic of salicylate from MgAl-LDH-SA hybrids in phosphate buffer saline (PBS) at pH7.4 showed a sustained release of salicylate up to 72h that closely resembled first order release kinetics through a combination of drug diffusion and dissolution of LDH under physiological conditions. Also the

  17. Direct handling of sharp interfacial energy for microstructural evolution

    SciTech Connect

    Hernández–Rivera, Efraín; Tikare, Veena; Noirot, Laurence; Wang, Lumin

    2014-08-24

    In this study, we introduce a simplification to the previously demonstrated hybrid Potts–phase field (hPPF), which relates interfacial energies to microstructural sharp interfaces. The model defines interfacial energy by a Potts-like discrete interface approach of counting unlike neighbors, which we use to compute local curvature. The model is compared to the hPPF by studying interfacial characteristics and grain growth behavior. The models give virtually identical results, while the new model allows the simulator more direct control of interfacial energy.

  18. Functionalization enhancement on interfacial shear strength between graphene and polyethylene

    NASA Astrophysics Data System (ADS)

    Jin, Yikuang; Duan, Fangli; Mu, Xiaojing

    2016-11-01

    Pull-out processes were simulated to investigate the interfacial mechanical properties between the functionalized graphene sheet (FGS) and polyethylene (PE) matrix by using molecular dynamics simulation with ReaxFF reactive force field. The interfacial structure of polymer and the interfacial interaction in the equilibrium FGS/PE systems were also analyzed to reveal the enhancement mechanism of interfacial shear strength. We observed the insertion of functional groups into polymer layer in the equilibrium FGS/PE systems. During the pull-out process, some interfacial chains were attached on the FGS and pulled out from the polymer matrix. The behavior of these pulled out chains was further analyzed to clarify the different traction action of functional groups applied on them. The results show that the traction effect of functional groups on the pulled-out chains is agreement with their enhancement influence on the interfacial shear strength of the FGS/PE systems. They both are basically dominated by the size of functional groups, suggesting the enhancement mechanism of mechanical interlocking. However, interfacial binding strength also exhibits an obvious influence on the interfacial shear properties of the hybrid system. Our simulation show that geometric constrains at the interface is the principal contributor to the enhancement of interfacial shear strength in the FGS/PE systems, which could be further strengthened by the wrinkled morphology of graphene in experiments.

  19. Interfacial welding of dynamic covalent network polymers

    NASA Astrophysics Data System (ADS)

    Yu, Kai; Shi, Qian; Li, Hao; Jabour, John; Yang, Hua; Dunn, Martin L.; Wang, Tiejun; Qi, H. Jerry

    2016-09-01

    Dynamic covalent network (or covalent adaptable network) polymers can rearrange their macromolecular chain network by bond exchange reactions (BERs) where an active unit replaces a unit in an existing bond to form a new bond. Such macromolecular events, when they occur in large amounts, can attribute to unusual properties that are not seen in conventional covalent network polymers, such as shape reforming and surface welding; the latter further enables the important attributes of material malleability and powder-based reprocessing. In this paper, a multiscale modeling framework is developed to study the surface welding of thermally induced dynamic covalent network polymers. At the macromolecular network level, a lattice model is developed to describe the chain density evolution across the interface and its connection to bulk stress relaxation due to BERs. The chain density evolution rule is then fed into a continuum level interfacial model that takes into account surface roughness and applied pressure to predict the effective elastic modulus and interfacial fracture energy of welded polymers. The model yields particularly accessible results where the moduli and interfacial strength of the welded samples as a function of temperature and pressure can be predicted with four parameters, three of which can be measured directly. The model identifies the dependency of surface welding efficiency on the applied thermal and mechanical fields: the pressure will affect the real contact area under the consideration of surface roughness of dynamic covalent network polymers; the chain density increment on the real contact area of interface is only dependent on the welding time and temperature. The modeling approach shows good agreement with experiments and can be extended to other types of dynamic covalent network polymers using different stimuli for BERs, such as light and moisture etc.

  20. Electron impact induced anion production in acetylene.

    PubMed

    Szymańska, Ewelina; Čadež, Iztok; Krishnakumar, E; Mason, Nigel J

    2014-02-28

    A detailed experimental investigation of electron induced anion production in acetylene, C2H2, in the energy range between 1 and 90 eV is presented. The anions are formed by two processes in this energy range: dissociative electron attachment (DEA) and dipolar dissociation (DD). DEA in C2H2 is found to lead to the formation of H(-) and C2(-)/C2H(-) through excitation of resonances in the electron energy range 1-15 eV. These anionic fragments are formed with super thermal kinetic energy and reveal no anisotropy in the angular distributions. DD in C2H2 leads to the formation of H(-), C(-)/CH(-) and C2(-)/C2H(-) with threshold energies of 15.7, 20.0 and 16.5 eV respectively. The measured anion yields have been used to calculate anion production rates for H(-), C(-)/CH(-) and C2(-)/C2H(-) in Titan's ionosphere. PMID:24343432