Science.gov

Sample records for hydroxide anion interfacial

  1. Hydroxide Solvation and Transport in Anion Exchange Membranes

    SciTech Connect

    Chen, Chen; Tse, Ying-Lung Steve; Lindberg, Gerrick E.; Knight, Chris; Voth, Gregory A.

    2016-01-27

    Understanding hydroxide solvation and transport in anion exchange membranes (AEMs) can provide important insight into the design principles of these new membranes. To accurately model hydroxide solvation and transport, we developed a new multiscale reactive molecular dynamics model for hydroxide in aqueous solution, which was then subsequently modified for an AEM material. With this model, we investigated the hydroxide solvation structure and transport mechanism in the membrane. We found that a relatively even separation of the rigid side chains produces a continuous overlapping region for hydroxide transport that is made up of the first hydration shell of the tethered cationic groups. Our results show that hydroxide has a significant preference for this overlapping region, transporting through it and between the AEM side chains with substantial contributions from both vehicular (standard diffusion) and Grotthuss (proton hopping) mechanisms. Comparison of the AEM with common proton exchange membranes (PEMs) showed that the excess charge is less delocalized in the AEM than the PEMs, which is correlated with a higher free energy barrier for proton transfer reactions. The vehicular mechanism also contributes considerably more than the Grotthuss mechanism for hydroxide transport in the AEM, while our previous studies of PEM systems showed a larger contribution from the Grotthuss mechanism than the vehicular mechanism for proton transport. The activation energy barrier for hydroxide diffusion in the AEM is greater than that for proton diffusion in PEMs, implying a more significant enhancement of ion transport in the AEM at elevated temperatures.

  2. Hydroxide Solvation and Transport in Anion Exchange Membranes.

    PubMed

    Chen, Chen; Tse, Ying-Lung Steve; Lindberg, Gerrick E; Knight, Chris; Voth, Gregory A

    2016-01-27

    Understanding hydroxide solvation and transport in anion exchange membranes (AEMs) can provide important insight into the design principles of these new membranes. To accurately model hydroxide solvation and transport, we developed a new multiscale reactive molecular dynamics model for hydroxide in aqueous solution, which was then subsequently modified for an AEM material. With this model, we investigated the hydroxide solvation structure and transport mechanism in the membrane. We found that a relatively even separation of the rigid side chains produces a continuous overlapping region for hydroxide transport that is made up of the first hydration shell of the tethered cationic groups. Our results show that hydroxide has a significant preference for this overlapping region, transporting through it and between the AEM side chains with substantial contributions from both vehicular (standard diffusion) and Grotthuss (proton hopping) mechanisms. Comparison of the AEM with common proton exchange membranes (PEMs) showed that the excess charge is less delocalized in the AEM than the PEMs, which is correlated with a higher free energy barrier for proton transfer reactions. The vehicular mechanism also contributes considerably more than the Grotthuss mechanism for hydroxide transport in the AEM, while our previous studies of PEM systems showed a larger contribution from the Grotthuss mechanism than the vehicular mechanism for proton transport. The activation energy barrier for hydroxide diffusion in the AEM is greater than that for proton diffusion in PEMs, implying a more significant enhancement of ion transport in the AEM at elevated temperatures.

  3. Layered double hydroxides as anion- and cation-exchanging materials

    NASA Astrophysics Data System (ADS)

    Richardson, Mickey Charles

    2007-12-01

    Layered double hydroxides (LDH) have been principally known as anion-exchanging, clay-like materials for several decades, and continues to be the main driving force for current and future research. The chemical interactions of LDH, with transition metallocyanides, have been a popular topic of investigation for many years, partly due to the use of powder x-ray diffraction and infrared spectroscopy as the main characterization tools. Each transition metallocyanide has a characteristic infrared stretching frequency that can be easily observed, and their respective sizes can be observed while intercalated within the interlayer of the LDH. The ability of LDH to incorporate metal cations or any ions/molecules/complexes, that have a postive charge, have not been previously investigated, mainly due to the chemical and physical nature of LDH. The possibility of cationic incorporation with LDH would most likely occur by surface adsorption, lattice metal replacement, or by intercalation into the LDH interlayers. Although infrared spectroscopy finds it main use through the identification of the anions incorporated with LDH, it can also be used to study and identify the various active and inactive bending and stretching modes that the metal hydroxide layers have.

  4. 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.

  5. 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

    2015-10-07

    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.

  6. Mg/Al double-metal hydroxide regeneration of anion exchange resin by electric field intensification.

    PubMed

    Wang, Ying; Li, Zhun; Li, Yansheng; Liu, Zhigang

    2017-03-01

    Fouled anion exchange resins were regenerated by electric field intensification of Mg/Al double-metal hydroxides. Regenerative experiments were performed with varying voltages (10-30 V) and dosages of Mg/Al hydroxides (0.045-0.135 mol and 0.015-0.045 mol, respectively) for 1-5 h. Optimal results were obtained under the following regenerative conditions: 20 V, 4 h, and 0.09/0.03 mol of Mg/Al hydroxides. The maximum regenerative capacity of resins was increased to 41.07%. The regenerative mechanism was presented by Fourier-transform infrared spectrum of resins and Mg/Al hydroxides, and the regenerative degree was analyzed with respect to conductivity, pH value, and electric current. Mg/Al hydroxides were also recycled after the regeneration. This method was proven to be cost-effective and environmentally friendly.

  7. Anion exchange kinetics of nanodimensional layered metal hydroxides: use of isoconversional analysis.

    PubMed

    Majoni, Stephen; Hossenlopp, Jeanne M

    2010-12-16

    Anion exchange reactions of nanodimensional layered metal hydroxide compounds are utilized to create materials with targeted physical and chemical properties and also as a means for controlled release of intercalated anions. The kinetics of this important class of reaction are generally characterized by model-based approaches. In this work, a different approach based on isothermal, isoconversional analysis was utilized to determine effective activation energies with respect to extent of reaction. Two different layered metal hydroxide materials were chosen for reaction with chloride anions, using a temperature range of 30-60 °C. The concentrations of anions released into solution and the changes in polycrystalline solid phases were evaluated using model-based (Avrami-Erofe'ev nucleation-growth model) and model-free (integral isoconversional) methods. The results demonstrate the utility of the isoconversional approach for identifying when fitting to a single model is not appropriate, particularly for characterizing the temperature dependence of the reaction kinetics.

  8. 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).

  9. Mg-Al layered double hydroxide intercalated with porphyrin anions: molecular simulations and experiments.

    PubMed

    Kovár, Petr; Pospísil, Miroslav; Káfunková, Eva; Lang, Kamil; Kovanda, Frantisek

    2010-02-01

    Molecular modeling in combination with powder X-ray diffraction (XRD) provided new information on the organization of the interlayer space of Mg-Al layered double hydroxide (LDH) containing intercalated porphyrin anions [5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS)]. Anion-exchange and rehydration procedures were used for the preparation of TPPS-containing LDH with an Mg/Al molar ratio of 2. Molecular modeling was carried out in the Cerius(2) and Materials Studio modeling environment. Three types of models were created in order to simulate the experimental XRD patterns of LDH intercalates with a TPPS loading of 70-80% with respect to the theoretical anion exchange capacity (AEC). The models represent single-phase systems with a 100% TPPS loading in the interlayer space (Type 1) and models represent the coexistence of two phases corresponding to the total exchange from 75 to 92% (Type 2). To cover other possible arrangements, models with the coexistence of both TPPS and NO(3)(-) anions in the same interlayer space were calculated (Type 3). The models are described and compared with experimental data. In all cases, guest TPPS anions are tilted with respect to the hydroxide layers, and are horizontally shifted to each other by up to one-half of the TPPS diameter. According to the energy characteristics and simulated XRD, the most probable arrangement is of Type 2, where some layers are saturated with TPPS anions and others are filled with original NO(3)(-) anions.

  10. [Sorption of nitrobenzene to anionic surfactant modified layered double hydroxides].

    PubMed

    Xia, Yan; Zhu, Run-Liang; Tao, Qi; Liu, Han-Yang

    2013-01-01

    Sodium dodecyl sulfate (SDS) modified MgAl layered double hydroxides (LDHs) were synthesized at different surfactant concentrations (0.5-2.0 TAEC) by the co-precipitation method. The LDH-DS samples obtained were characterized by powder X-ray diffraction and FT-IR spectroscopy. The results showed that SDS was successfully intercalated into the interlayer of the LDH, and the basal spacing was expanded from 0.80 nm to 3.98 nm. The intercalated SDS was considered consistent with a paraffin bilayers arrangement. The sorption of nitrobenzene on LDH-DS was examined, and the results showed that linear model could fit the sorption isotherms well (R2 > 0.99), which implied a partitioning sorption process. The sorption coefficient of nitrobenzene (K(d)) on LDH-DS was positively related to the DS - loading amount, but the organic carbon content normalized sorption coefficient of nitrobenzene (K(oc)) was shown to remain relatively constant. The sorption thermodynamics results showed that the sorption of nitrobenzene on LDH-DS was an endothermic process, and the increase of entropy was the driving force for the sorption process.

  11. 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.

  12. Intracellular release of fluorescein anion from layered double hydroxide nanoparticles indicating endosomal escape

    NASA Astrophysics Data System (ADS)

    Tanaka, M.; Aisawa, S.; Hidetoshi, H.; Narita, E.; Dong, Q.; Yin, S.; Sato, T.

    2013-12-01

    In recent years, layered double hydroxide (LDH) has been attempted to be applied to a molecular container due to their anion exchange ability, low cytotoxicity and good biocompatibility. In this paper, we investigated the intracellular behaviour of LDH particles in mammalian cells after internalization. Nanoparticles of fluorescein (Fluo) intercalated LDH, Fluo/LDH, were prepared by the coprecipitation followed by subsequent hydrothermal treatment. As-prepared Fluo/LDH particles have the LDH structure and morphology of hexagonal sheet of 100 nm on the average. In addition, Fluo/LDH also exhibited high green fluorescence and low cytotoxicity. By a confocal laser scanning microscopy, the dim green fluorescence was observed throughout cells, including the nucleus. This result indicated that Fluo/LDH released guest anion (Fluo) from LDH structure inside cells. Furthermore, because the fluorescence was observed throughout the cell, Fluo was not retained within endosome structure, i.e., Fluo/LDH was dissolved to release Fluo from endosome.

  13. 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.

  14. 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.

  15. 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

  16. Microwave-assisted melt reaction method for the intercalation of carboxylic acid anions into layered double hydroxides.

    PubMed

    Rosa, Roberto; Leonelli, Cristina; Villa, Carla; Priarone, Giulia

    2013-01-01

    Carboxylic acid anions intercalated layered double hydroxides are currently gaining increasing interest due to their potential applications in pharmaceutical field for controlled drug release in novel tunable drug delivery systems. In this work different aliphatic carboxylic acid anions were intercalated into the interlayers of commercial as well as synthetically prepared layered double hydroxides, through a novel microwave mediated melt reaction approach. The volumetric nature of microwave dielectric heating was exploited in order to rapidly heat the intimate mixture of the lamellar inorganic precursor and the appropriate organic acid, at the melting temperature of the particular mono- or dicarboxylic acid used, reaching the intercalation in approximately two hours treatment.

  17. Ultrathin nanofibrous films prepared from cadmium hydroxide nanostrands and anionic surfactants.

    PubMed

    Peng, Xinsheng; Karan, Santanu; Ichinose, Izumi

    2009-08-04

    We developed a simple fabrication method of ultrathin nanofibrous films from the dispersion of cadmium hydroxide nanostrands and anionic surfactants. The nanostrands were prepared in a dilute aqueous solution of cadmium chloride by using 2-aminoethanol. They were highly positively charged and gave bundlelike fibers upon mixing an aqueous solution of anionic surfactant. The nanostrand/surfactant composite fibers were filtered on an inorganic membrane filter. The resultant nanofibrous film was very uniform in the area of a few centimeters square when the thickness was not less than 60 nm. The films obtained with sodium tetradecyl sulfate (STS) had a composition close to the electroneutral complex, [Cd37(OH)68(H2O)n] x 6(STS), as confirmed by energy dispersive X-ray analysis. They were water-repellent with a contact angle of 117 degrees, and the value slightly decreased with the alkyl chain length of anionic surfactants. Ultrathin nanofibrous films were stable enough to be used for ultrafiltration at pressure difference of 90 kPa. We could effectively separate Au nanoparticles of 40 nm at an extremely high filtration rate of 14000 L/(h m2 bar).

  18. Nickel-based layered double hydroxide from guest vanadium oxide anions

    NASA Astrophysics Data System (ADS)

    Park, Hae Woong; Chae, Ji Su; Park, Sun-Min; Kim, Kwang-Bum; Roh, Kwang Chul

    2013-07-01

    The layered double hydroxides (LDHs) are well known for ionic exchange properties to intercalate anionic compound in interlayer region. The Ni/V LDH composite was explored by co-precipitation method. The maximum capacitance of Ni/V LDH composite was 2612 F g-1 at the scan rate 2 mV s-1. As-synthesized Ni/V LDH composite provides a three-dimensional conducting network frame for manifesting electrochemical capacitance. This is because the insertion of vanadium oxide anions (VOx -) into nickel interlayer space between nickel layers is compensated for hydroxyl vacancies during synthesis of lower-pH condition. The network frame makes it possible to promote fast electron transfer for Ni/V LDH composite electrode material and consequently allows the improvement of the electronic conductivity for Ni/V LDH composite electrode material. Thus, the Ni/V LDH composite exhibits high capacitance than β-Ni(OH)2 due to its unique properties, with vanadium oxide anions embedded in the turbostratic structure and shorter diffusion pathway.

  19. Layered double hydroxides as the next generation inorganic anion exchangers: Synthetic methods versus applicability.

    PubMed

    Chubar, Natalia; Gilmour, Robert; Gerda, Vasyl; Mičušík, Matej; Omastova, Maria; Heister, Katja; Man, Pascal; Fraissard, Jacques; Zaitsev, Vladimir

    2017-07-01

    This work is the first report that critically reviews the properties of layered double hydroxides (LDHs) on the level of speciation in the context of water treatment application and dynamic adsorption conditions, as well as the first report to associate these properties with the synthetic methods used for LDH preparation. Increasingly stronger maximum allowable concentrations (MAC) of various contaminants in drinking water and liquid foodstuffs require regular upgrades of purification technologies, which might also be useful in the extraction of valuable substances for reuse in accordance with modern sustainability strategies. Adsorption is the main separation technology that allows the selective extraction of target substances from multicomponent solutions. Inorganic anion exchangers arrived in the water business relatively recently to achieve the newly approved standards for arsenic levels in drinking water. LDHs (or hydrotalcites, HTs) are theoretically the best anion exchangers due to their potential to host anions in their interlayer space, which increases their anion removal capacity considerably. This potential of the interlayer space to host additional amounts of target aqueous anions makes the LDHs superior to bulk anion exchanger. The other unique advantage of these layered materials is the flexibility of the chemical composition of the metal oxide-based layers and the interlayer anions. However, until now, this group of "classical" anion exchangers has not found its industrial application in adsorption and catalysis at the industrial scale. To accelerate application of LDHs in water treatment on the industrial scale, the authors critically reviewed recent scientific and technological knowledge on the properties and adsorptive removal of LDHs from water on the fundamental science level. This also includes review of the research tools useful to reveal the adsorption mechanism and the material properties beyond the nanoscale. Further, these properties are

  20. 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.

  1. 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.

  2. DNA Release from Lipoplexes by Anionic Lipids: Correlation with Lipid Mesomorphism, Interfacial Curvature, and Membrane Fusion

    PubMed Central

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

    2004-01-01

    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. PMID:15298910

  3. 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.

  4. Ion exchange and intercalation properties of layered double hydroxides towards halide anions.

    PubMed

    Costantino, Umberto; Vivani, Riccardo; Bastianini, Maria; Costantino, Ferdinando; Nocchetti, Morena

    2014-08-14

    A layered double hydroxide (LDH) obtained by the urea method, having an empirical formula [Zn(0.61)Al(0.39)(OH)2](CO3)(0.195)·0.50H2O, has been converted into the corresponding chloride form [Zn(0.61)Al(0.39)(OH)2]Cl(0.39)·0.47H2O by making the solid come into contact with a suitable HCl solution. The intercalation of the other halide anions (X(-) = F(-), Br(-), I(-)) via the Cl(-)/X(-) anion exchange has been attained and the respective anion exchange isotherms have been obtained with the batch method. The analysis of the isotherms indicates that the selectivity of LDH towards the halides decreases with the increase of the X(-) ionic radius, the selectivity order being F(-) > Cl(-)≥ Br(-) > I(-). The CO3(2-)/Cl(-) isotherm has also been reported to highlight the extraordinary selectivity of LDH towards carbonate anions. Samples taken from the isotherms at different exchange degrees were analyzed by X-ray diffraction, thermogravimetry and thermodiffractometry to obtain information about the ion exchange mechanism. The Cl(-)/Br(-) and the reverse Br(-)/Cl(-) exchanges occur with the formation of solid solutions, very likely because of the similar ionic radius of the exchanging anions. In contrast, in the Cl(-)/F(-) and Cl(-)/I(-) exchange, the co-existence of the Cl(-) and F(-) (or I(-)) phases in the same sample was detected, indicating the occurrence of a first order phase transition, in which the starting phase is transformed into the final phase, as the process goes on. The variation of the interlayer distances of ZnAl-X intercalation compounds with the hydration degree has been interpreted with a structural model based on the nesting of the guest species into the trigonal pockets of the brucite-like layer surface. Rietveld refinements of the phases with the maximum F(-), Br(-) and I(-) content were also performed and compared with the above model, giving indications of the arrangement and order/disorder of the halide anions in the interlayer region.

  5. Anion exchange reaction potentials as approximate estimates of the relative thermodynamic stabilities of Mg/Al layered double hydroxides containing different anions.

    PubMed

    Prasad, Belavalli E; Kamath, P Vishnu; Vijayamohanan, K

    2011-11-15

    Coatings of hydrotalcite-like nitrate-intercalated Mg/Al layered double hydroxides are electrochemically deposited on a Pt electrode by electrogeneration of base by reduction of a mixed metal nitrate aqueous solution. As-prepared coatings are stable to workup and function as rugged electrodes. The voltammetric response generated by anion exchange of intercalated nitrate for dissolved anions from solution under equilibrium conditions is employed to estimate the thermodynamic stabilities of the Mg/Al layered double hydroxides comprising different anions relative to the nitrate-containing phase. Among monovalent anions, the most stable is the fluoride-containing LDH (ΔG° = -48.7 kJ mol(-1)) relative to the nitrate-containing LDH. The stability in aqueous phase decreases as F(-) > Cl(-) > Br(-) > NO(2)(-) > NO(3)(-), whereas, among divalent anions, SO(4)(2-) (ΔG° = -8.7 kJ mol(-1)) > CO(3)(2-) (ΔG° = 14.3 kJ mol(-1)). The results of monovalent ions match well with the Miyata series, whereas the divalent anion series is at variance with the commonly held belief that carbonate-LDHs are more stable than sulfate-LDHs.

  6. Facile assembly for fast construction of intercalation hybrids of layered double hydroxides with anionic metalloporphyrin.

    PubMed

    Ma, Juanjuan; Liu, Lin; Li, Shanzhong; Chen, Yonghao; Zhuo, Meng; Shao, Feng; Gong, Junyan; Tong, Zhiwei

    2014-07-14

    Anionic manganese tetrasulfonatophenyl porphyrin (MnTSPP) has been intercalated into the interlamellar space of Mg-Al and Ni-Al layered double hydroxides (LDHs) through the exfoliation/restacking approach by using exfoliated LDH nanosheets and guest molecules as building blocks. The obtained hybrids were characterized by a variety of analytical techniques such as CHN analysis, XRD, FTIR, SEM, HRTEM, UV-vis spectroscopy and thermal analysis. Interlayer spacings determined from XRD patterns reveal a perpendicular orientation of the MnTSPP anions between the hyroxylated layers of both LDHs. The results of zeta potential measurements give information about the surface charge change of LDH nanoparticles associated with the spontaneous coassembly process. The catalytic performance of the heterogeneous catalysts MnTSPP/Mg-Al LDH2.0 and MnTSPP/Ni-Al LDH1.0 for the epoxidation of cyclohexene was investigated using molecular oxygen as an oxidant and isobutylaldehyde as a co-reductant. The intercalated hybrids appear to be promising catalysts owing to their good catalytic activity and selectivity.

  7. 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.

  8. 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.

  9. Effect of adsorbed/intercalated anionic dyes into the mechanical properties of PVA: layered zinc hydroxide nitrate nanocomposites.

    PubMed

    Marangoni, Rafael; Mikowski, Alexandre; Wypych, Fernando

    2010-11-15

    Zinc hydroxide nitrate (ZHN) was adsorbed with anions of blue dyes (Chicago sky blue, CSB; Evans blue, EB; and Niagara blue, NB) and intercalated with anions of orange dyes (Orange G, OG; Orange II, OII; methyl orange, MO). Transparent, homogeneous and colored nanocomposite films were obtained by casting after dispersing the pigments (dye-intercalated/adsorbed into LHSs) into commercial poly(vinyl alcohol) (PVA). The films were characterized by XRD, UV-Vis spectroscopy, and mechanical testing. The mechanical properties of the PVA compounded with the dye-intercalated/adsorbed ZHN were evaluated, and reasonable increases in Young's modulus and ultimate tensile strength were observed, depending on the amount and choice of layered filler. These results demonstrate the possibility of using a new class of layered hydroxide salts intercalated and adsorbed with anionic dyes to prepare multifunctional polymer nanocomposite materials. Copyright © 2010 Elsevier Inc. All rights reserved.

  10. Magnetic cellulose ionomer/layered double hydroxide: An efficient anion exchange platform with enhanced diclofenac adsorption property.

    PubMed

    Hossein Beyki, Mostafa; Mohammadirad, Mosleh; Shemirani, Farzaneh; Saboury, Ali Akbar

    2017-02-10

    Polymeric ionomers with anion exchange capability are considered to be classes of environmentally friendly compounds as combination of them with anionic layered hydroxides constitute emerging advance materials. Biosorption by polymeric ionomer - layered double hydroxide (LDH) hybrid material exhibits an attractive green, low cost and low toxic - clean way. As a result, a novel anion exchange platform has been developed by the reaction of CaAl - LDH with Fe(2+), cellulose solution, epichlorohydrin and pyridine. Magnetite cellulose - LDH (MCL) and the ionomer were used for efficient biosorption of diclofenac sodium (DF). Results showed that ionomer has more efficiency for DF adsorption relative to MCL. Magnetite ionomer showed fast equilibrium time (2min) with maximum uptake of 268mgg(-1). Isotherm and Kinetic models were also studied. Regeneration of the sorbent was performed with a mixture of methanol -NaOH (2.0molL(-1)) solution.

  11. 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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. A review of the removal of anions and oxyanions of the halogen elements from aqueous solution by layered double hydroxides.

    PubMed

    Theiss, Frederick L; Couperthwaite, Sara J; Ayoko, Godwin A; Frost, Ray L

    2014-03-01

    The application of layered double hydroxides (LDHs) and thermally activated LDHs for the removal of various fluorine (F(-),BF4(-)), chlorine (Cl(-),ClO4(-)), bromine (Br(-),BrO3(-)) and iodine (I(-),IO3(-)) species from aqueous solutions has been reviewed in this article. LDHs and thermally activated LDHs were able to significantly reduce the concentration of selected anions in laboratory scale experiments. The M(2+):M(3+) cation ratio of the LDH adsorbent was an important factor which influenced anion uptake. Though LDHs were able to remove some target anion species through anion exchange and surface adsorption thermal activation and reformation generally produced better results. The presence of competing anions including carbonate, phosphate and sulphate had a significant impact on uptake of the target anion as LDHs typically exhibit lower affinity towards monovalent anions compared to anions with multiple charges. The removal of fluoride and perchlorate from aqueous solution by a continuous flow system utilising fixed bed columns packed with LDH adsorbents has also been investigated. The adsorption capacity of the columns at breakpoint was heavily dependent on the flow rate and lower than result reported for the corresponding batch methods. There is still considerable scope for future research on numerous topics summarised in this article. Copyright © 2013 Elsevier Inc. All rights reserved.

  13. In situ dielectric measurements of Zn?Al layered double hydroxide with anionic nitrate ions

    NASA Astrophysics Data System (ADS)

    Ahmed, Abdullah Ahmed Ali; Talib, Zainal Abidin; Hussein, Mohd Zobir bin; Zakaria, Azmi

    2012-08-01

    Zn-Al-NO3-layered double hydroxide (Zn-Al-NO3-LDH) was prepared by the co-precipitation method with a ratio of Zn/Al = 4 and at a constant pH of 7. Powder XRD patterns showed the characteristic peaks of layered structure of the LDH sample. Thermogravimetric analysis (TGA) and infrared spectra of the sample were investigated. Because of the existence of water molecules and anionic NO3- in the interlayer of the LDH, the in situ dielectric spectroscopy of the LDH can be described by an anomalous low frequency dispersion using the second type of Universal Power Law. Novel measurements of activation energy of LDH have been obtained at five different frequencies. The energy value increased from 0.05 eV at 1 MHz to 0.37 eV at 134 Hz. The conductivity spectra of sample were studied as a function in temperature of the in situ measurements. The ionic conductivity (dc) of LDH increased as the in situ temperature increased.

  14. Exchange of interlayer terephthalate anions from a Mg Al layered double hydroxide: formation of intermediate interstratified phases

    NASA Astrophysics Data System (ADS)

    Kaneyoshi, Masami; Jones, William

    1998-10-01

    The exchange of interlayer terephthalate (TA) anions from a Mg-Al layered double hydroxide (LDH) by carbonate, sulfate, chloride and nitrate anions is reported. It is shown that TA is readily exchanged by CO 32- and SO 42- but only partly by Cl - and NO 3-. We demonstrate that during the exchange process interstratified phases are observed. Such interstratification has previously been reported only for directly synthesised materials. The origin of the interstratification is believed to be associated with two preferred orientations of TA anions within the layers, i.e. vertical or horizontal to the clay sheets. Two models for the possible exchange mechanism which is operating in these systems are proposed.

  15. Removal of chloride ion from aqueous solution by ZnAl-NO(3) layered double hydroxides as anion-exchanger.

    PubMed

    Lv, Liang; Sun, Peide; Gu, Zhengyu; Du, Hangeng; Pang, Xiangjun; Tao, Xiaohong; Xu, Rufeng; Xu, Lili

    2009-01-30

    The layered double hydroxides (LDHs) containing nitrate as the interlayer anion has a high anion-exchange capacity in the presence of appropriate anions. In the light of this, ZnAl-NO(3) LDHs have been employed to remove chloride ion from aqueous solution in a batch mode. The influences of conditions for chloride ion uptake, including dosage of LDHs, pH of aqueous solution, and temperature on anion-exchange have been investigated, respectively. The thermodynamic parameters including Gibbs free energy (DeltaG(0)), standard enthalpy change (DeltaH(0)), and standard entropy change (DeltaS(0)) for the process were calculated using the Langmuir constants. It was found from kinetics test that the pseudo-second order kinetics model could be used to well describe the uptake process. An E(a) value of 10.27 kJ/mol provides evidence the anion-exchange process. The explanation of anion-exchange phenomenon has also been supported by X-ray diffraction and FT-IR spectra.

  16. 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.

  17. closo-Dodecaborate Intercalated Yttrium Hydroxide as a First Example of Boron Cluster Anion-Containing Layered Inorganic Substances.

    PubMed

    Yapryntsev, Alexey D; Bykov, Alexander Yu; Baranchikov, Alexander E; Zhizhin, Konstantin Yu; Ivanov, Vladimir K; Kuznetsov, Nikolay T

    2017-03-03

    The first member, Y2(OH)5.46(B12H12)0.23Cl0.08·4.98H2O, of a new family of boron-containing substances, closo-dodecaborate intercalated layered rare-earth hydroxides, was synthesized using a microwave-assisted hydrothermal method. The structure and composition of this compound were studied by X-ray diffraction, transmission and scanning electron microscopy, thermal analysis, inductively coupled plasma mass spectrometry, IR spectroscopy, and X-ray photoelectron spectroscopy. The title compound had the composition Y2(OH)5.46(B12H12)0.23Cl0.08·4.98H2O and crystallized in a form of plate-like, aggregated particles less than 10 nm thick. The coordination of closo-dodecaborate anions with yttrium hydroxide host layers was demonstrated.

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

    NASA Astrophysics Data System (ADS)

    Watanabe, Mebae; Fujihara, Shinobu

    2014-02-01

    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 Eu3+ ions, the LYHs exhibited red photoluminescence which was enhanced by the intercalated anions due to the antenna effect.

  19. Fulvic acid anchored layered double hydroxides: A multifunctional composite adsorbent for the removal of anionic dye and toxic metal.

    PubMed

    Li, Lei; Qi, Guangxia; Wang, Bangda; Yue, Dongbei; Wang, Yi; Sato, Tsutomu

    2017-09-06

    A novel multifunctional composite adsorbent which possesses the ability for anion exchange and toxic metal complexation has been synthesized by the hybridization of layered double hydroxides (LDH) and fulvic acid (FA) in this study. The results show that FA with lots of functional groups can be effectively and stably anchored on the surface of LDH through coagulation process without occupying the interlayer of LDH. Therefore, the anion exchange ability remains and the adsorption capacity of Orange II can reach 1.9mmol/g, which is almost as much as stoichiometric anion exchange capacity of pure LDH. Moreover, the composite adsorbent's adsorption capacity of Cu(2+), Pb(2+), Ni(2+) and Cd(2+) can also get to 2.25mmol/g, 0.98mmol/g, 0.99mmol/g and 0.16mmol/g respectively with an adsorption preference order of Cu(2+)>Pb(2+)>Ni(2+)>Cd(2+). In addition, Orange II and toxic metals are able to be simultaneously removed by this composite adsorbent, and the adsorption of toxic metals can be enhanced by the synergetic adsorption of Orange II. Anion exchange with Cl(-) in LDH matrix accounts for the adsorption of Orange II, while the adsorption of toxic metal is mainly attributed to the complexation of carboxyl functional group derived from FA. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Formation of periodic interfacial misfit dislocation array at the InSb/GaAs interface via surface anion exchange

    NASA Astrophysics Data System (ADS)

    Jia, Bo Wen; Tan, Kian Hua; Loke, Wan Khai; Wicaksono, Satrio; Yoon, Soon Fatt

    2016-07-01

    The relationship between growth temperature and the formation of periodic interfacial misfit (IMF) dislocations via the anion exchange process in InSb/GaAs heteroepitaxy was systematically investigated. The microstructural and electrical properties of the epitaxial layer were characterized using atomic force microscope, high-resolution x-ray diffraction, transmission electron microscopy, and Hall resistance measurement. The formation of interfacial misfit (IMF) dislocation arrays depended on growth temperature. A uniformly distributed IMF array was found in a sample grown at 310 °C, which also exhibited the lowest threading dislocation density. The analysis suggested that an incomplete As-for-Sb anion exchange process impeded the formation of IMF on sample grown above 310 °C. At growth temperature below 310 °C, island coalescence led to the formation of 60° dislocations and the disruption of periodic IMF array. All samples showed higher electron mobility at 300 K than at 77 K.

  1. 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.

  2. 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.

  3. Nanohybrids of Mg/Al layered double hydroxide and long-chain (C18) unsaturated fatty acid anions: Structure and sorptive properties

    USDA-ARS?s Scientific Manuscript database

    Long-chain (C18) unsaturated fatty acid anions, elaidate (ELA), oleate (OLE), linoleate (LINO), and linolenate (LINOLEN), were intercalated into Mg/Al (3:1) layered double hydroxide (LDH) and the resultant organo-LDH nanohybrid materials were characterized and subsequently evaluated as sorbents of s...

  4. Anion-exchange membranes derived from quaternized polysulfone and exfoliated layered double hydroxide for fuel cells

    NASA Astrophysics Data System (ADS)

    Liu, Wan; Liang, Na; Peng, Pai; Qu, Rong; Chen, Dongzhi; Zhang, Hongwei

    2017-02-01

    Layered double hydroxides (LDH) are prepared by controlling urea assisted homogeneous precipitation conditions. Morphology and crystallinity of LDHs are confirmed by X-ray diffraction and scanning electron microscope. After LDHs are incorporated into quaternized polysulfone membranes, transmission electron microscope is used to observe the exfoliated morphology of LDH sheets in the membranes. The properties of the nanocomposite membranes, including water uptake, swelling ratio, mechanical property and ionic conductivity are investigated. The nanocomposite membrane containing 5% LDH sheets shows more balanced performances, exhibiting an ionic conductivity of 2.36×10-2 S cm-1 at 60 °C.

  5. Layered double hydroxides as effective carrier for anticancer drugs and tailoring of release rate through interlayer anions.

    PubMed

    Senapati, Sudipta; Thakur, Ravi; Verma, Shiv Prakash; Duggal, Shivali; Mishra, Durga Prasad; Das, Parimal; Shripathi, T; Kumar, Mohan; Rana, Dipak; Maiti, Pralay

    2016-02-28

    Hydrophobic anticancer drug, raloxifene hydrochloride (RH) is intercalated into a series of magnesium aluminum layered double hydroxides (LDHs) with various charge density anions through ion exchange technique for controlled drug delivery. The particle nature of the LDH in presence of drug is determined through electron microscopy and surface morphology. The release of drug from the RH intercalated LDHs was made very fast or sustained by altering the exchangeable anions followed by the modified Freundlich and parabolic diffusion models. The drug release rate is explained from the interactions between the drug and LDHs along with order-disorder structure of drug intercalated LDHs. Nitrate bound LDH exhibits greater interaction with drug and sustained drug delivery against the loosely interacted phosphate bound LDH-drug, which shows fast release. Cell viability through MTT assay suggests drug intercalated LDHs as better drug delivery vehicle for cancer cell line against poor bioavailability of the pure drug. In vivo study with mice indicates the differential tumor healing which becomes fast for greater drug release system but the body weight index clearly hints at damaged organ in the case of fast release system. Histopathological experiment confirms the damaged liver of the mice treated either with pure drug or phosphate bound LDH-drug, fast release system, vis-à-vis normal liver cell morphology for sluggish drug release system with steady healing rate of tumor. These observations clearly demonstrate that nitrate bound LDH nanoparticle is a potential drug delivery vehicle for anticancer drugs without any side effect.

  6. Zn2Al layered double hydroxides intercalated and adsorbed with anionic blue dyes: a physico-chemical characterization.

    PubMed

    Marangoni, Rafael; Bouhent, Mustapha; Taviot-Guého, Christine; Wypych, Fernando; Leroux, Fabrice

    2009-05-01

    Three different anionic blue organic dyes have been intercalated into the structure of Zn(2)Al layered double hydroxides, using the co-precipitation method at constant pH. Using the same synthetic procedure, Zn(2)Al-Cl has been prepared and used as an adsorptive phase to retain the blue dyes from an aqueous solution. All the organic/inorganic (O/I) hybrid LDH compounds were analyzed by X-ray powder diffraction (XRPD), thermal analysis (TG/DTA), elemental analysis, solid state (13)C nuclear magnetic resonance (CPMAS (13)C NMR), and Fourier transform infrared spectroscopy (FTIR). In the adsorption experiments, Gibbs free energy DeltaG values for the temperatures in a range between 10 and 40 degrees C were found to be negative, which indicates that the nature of adsorption is spontaneous and shows the affinity of LDH material towards the blue anionic dyes. Additionally a decrease in DeltaG values at higher temperature further indicates that this process is even more favorable at these conditions. The enthalpy DeltaH values were between physisorption and chemisorption, and it may be concluded that the process was a physical adsorption enhanced by a chemical effect, characterized by a combined adsorption/intercalation reaction, making these O/I assemblies reminiscent of the Maya blue.

  7. Adsorption study of anionic reactive dye from aqueous solution to Mg-Fe-CO3 layered double hydroxide (LDH)

    NASA Astrophysics Data System (ADS)

    Ahmed, I. M.; Gasser, M. S.

    2012-10-01

    Mg-Fe-Cl Layered double hydroxides (LDHs) have been prepared using a method involving separate nucleation and aging steps with Mg/Fe = 3. The interlayer anions readily replaced by carbonate are characterized by X-ray diffraction (XRD) and FTIR. The effects of different parameters, such as pH, contact time, concentration of dye and temperature on the capacity and adsorption mechanism of Mg-Fe-CO3-LDH in removing an anionic dye (congo red, CR) from aqueous solution were separately investigated. The results show that Mg-Fe-CO3-LDH is particularly efficient in removing CR and the dye removal increases with decreasing pH. The adsorption of CR on Mg-Fe-CO3-LDH reached equilibrium after 15 min where 100 mg/L CR was removed. The equilibrium isotherm indicates that the adsorption of CR onto Mg-Fe-CO3-LDH fits to Langmuir and Freundlich equation as well. The adsorption data obtained from the Langmuir model gave good values of the determination coefficient and the saturated adsorption capacity of Mg-Fe-CO3-LDH for CR was found to be 104.6 mg/g. The regeneration study indicates that the prepared LDH could be used for several cycles. The thermodynamic parameters have been calculated, and the adsorption process was found to be spontaneous, endothermic in nature and follows a pseudo-second-order kinetic model.

  8. Design and fabrication of enhanced corrosion resistance Zn-Al layered double hydroxides films based anion-exchange mechanism on magnesium alloys

    NASA Astrophysics Data System (ADS)

    Zhou, Meng; Yan, Luchun; Ling, Hao; Diao, Yupeng; Pang, Xiaolu; Wang, Yanlin; Gao, Kewei

    2017-05-01

    Layered double hydroxides (LDHs) with brucite-like layer structure and the facile exchangeability of intercalated anions had attracted tremendous interest in many fields because of their great importance for both fundamental studies and practical applications. Herein zinc-aluminum layered double hydroxides (Zn-Al LDHs) films intercalated with nitrate anions on the magnesium alloy substrate were designed and fabricated via a facile hydrothermal crystallization method. In order to obtain better corrosion resistance, chloride and vanadate anions were intercalated into the LDHs interlayers via the anion-exchange reaction. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM) were used to examine structure, composition and morphology of the Zn-Al-NO3 LDHs, Zn-Al-Cl LDHs and Zn-Al-VOx LDHs films. The corrosion resistance of the Zn-Al LDHs with different anion films was estimated by the electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurement. EIS and polarization curves measurements revealed that the magnesium alloy could be effectively protected by the Zn-Al-Cl LDHs and Zn-Al-VOx LDHs films due to the blocking effect of chloride anions and the control-release ability of vanadate anions.

  9. Layered double hydroxides intercalated with anionic surfactants/benzophenone as potential materials for sunscreens.

    PubMed

    Cursino, Ana Cristina Trindade; Lisboa, Fábio da Silva; Pyrrho, Alexandre dos Santos; de Sousa, Valeria Pereira; Wypych, Fernando

    2013-05-01

    Layered double hydroxides intercalated with dodecylsulfate or dodecylbenzenesulfonate were synthesized by co-precipitation under alkaline conditions. After characterization by PXRD, FTIR, and TGA/DTA, the ZnxAl/SUR compounds were reacted with neutral benzophenone, using different procedures. The products obtained from benzophenone adsolubilization were investigated by PXRD, FTIR, and DRUV-Vis spectroscopy before and after exposure to UV radiation. In general, the content of adsolubilized benzophenone was small and depended on the synthetic procedure. The best results were achieved under microwave irradiation, which furnished 9.09 wt% adsolubilized benzophenone. The products presented good adsorption in the full UV region, from UVC to UVA, and good stability to UV radiation. They did not cause skin irritation in tests conducted on rabbits, which makes them good candidates for the development of a new generation of sunscreens. Copyright © 2013 Elsevier Inc. All rights reserved.

  10. Ab initio study of the neutral and anionic alkali and alkaline earth hydroxides: Electronic structure and prospects for sympathetic cooling of OH().

    PubMed

    Kas, Milaim; Loreau, Jérôme; Liévin, Jacques; Vaeck, Nathalie

    2017-05-21

    We have performed a systematic ab initio study on alkali and alkaline earth hydroxide neutral (MOH) and anionic (MOH(-)) species where M = Li, Na, K, Rb, Cs or Be, Mg, Ca, Sr, Ba. The CCSD(T) method with extended basis sets and Dirac-Fock relativistic effective core potentials for the heavier atoms has been used to study their equilibrium geometries, interaction energies, electron affinities, electric dipole moment, and potential energy surfaces. All neutral and anionic species exhibit a linear shape with the exception of BeOH, BeOH(-), and MgOH(-), for which the equilibrium structure is found to be bent. Our analysis shows that the alkaline earth hydroxide anions are valence-bound whereas the alkali hydroxide anions are dipole bound. In the context of sympathetic cooling of OH(-) by collision with ultracold alkali and alkaline earth atoms, we investigate the 2D MOH(-) potential energy surfaces and the associative detachment reaction M + OH→- MOH + e(-), which is the only energetically allowed reactive channel in the cold regime. We discuss the implication for the sympathetic cooling of OH(-) and conclude that Li and K are the best candidates for an ultracold buffer gas.

  11. 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%. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Formation of periodic interfacial misfit dislocation array at the InSb/GaAs interface via surface anion exchange

    SciTech Connect

    Jia, Bo Wen; Tan, Kian Hua; Loke, Wan Khai; Wicaksono, Satrio; Yoon, Soon Fatt

    2016-07-21

    The relationship between growth temperature and the formation of periodic interfacial misfit (IMF) dislocations via the anion exchange process in InSb/GaAs heteroepitaxy was systematically investigated. The microstructural and electrical properties of the epitaxial layer were characterized using atomic force microscope, high-resolution x-ray diffraction, transmission electron microscopy, and Hall resistance measurement. The formation of interfacial misfit (IMF) dislocation arrays depended on growth temperature. A uniformly distributed IMF array was found in a sample grown at 310 °C, which also exhibited the lowest threading dislocation density. The analysis suggested that an incomplete As-for-Sb anion exchange process impeded the formation of IMF on sample grown above 310 °C. At growth temperature below 310 °C, island coalescence led to the formation of 60° dislocations and the disruption of periodic IMF array. All samples showed higher electron mobility at 300 K than at 77 K.

  13. On the infrared absorption spectrum of the hydrated hydroxide (H3O2-) cluster anion

    NASA Astrophysics Data System (ADS)

    Peláez, Daniel; Meyer, Hans-Dieter

    2017-01-01

    In this work, we present an MCTDH simulation of the infrared (IR) spectrum of the H3O2- cluster anion and compare it to the Ar vibrational predissociation experimental one. In particular, we have focused on the 600-1900cm-1 energy region, which is the lowest energy region experimentally accessible. The computed bands have been assigned to the corresponding eigenstates. The latter have been obtained through Block Improved Relaxation calculations. An overall very good agreement between theory and experiment is achieved. However, certain discrepancies between the calculated IR and the experimental Ar vibrational predissociation one exist. We provide evidence that they are due to the influence of the attached Ar atom.

  14. A comparative study of structural and electrochemical properties of high-density aluminum substituted α-nickel hydroxide containing different interlayer anions

    NASA Astrophysics Data System (ADS)

    Shangguan, Enbo; Li, Jing; Guo, Dan; Guo, Litan; Nie, Mengzhen; Chang, Zhaorong; Yuan, Xiao-Zi; Wang, Haijiang

    2015-05-01

    Al-substituted α-type nickel hydroxides (α-Ni(OH)2) containing different interlayer anions (NO3-, SO42- , Cl-, CO32- , OH-) are synthesized via a polyacrylamide (PAM) assisted two-step drying method. The effects of interlayer anions on the microstructure, morphology and electrochemical performance of Al-substituted α-Ni(OH)2 are investigated by X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscope (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge/discharge tests. The results demonstrate that the intercalated anions have a critical effect on the basal plane spacing, degree of crystallinity, and electrochemical properties of the end products. Especially, the intercalated anions have a marked impact on the activation process of the nickel electrodes. The Cl- intercalated α-Ni(OH)2 sample exhibits better high-rate discharge ability and cycle stability than samples with other interlayer anions. This is attributed to the higher crystallinity, better exchange ability and smaller anion size of Cl-. The anion exchange ability and the size of anions also play an important role in the proton diffusion rate, which directly affects the electrochemical properties of α-Ni(OH)2. The relationships between the specific capacity and basal spacing are also discussed in details for the five samples.

  15. 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.

  16. Cu2+ ions as a paramagnetic probe to study the surface chemical modification process of layered double hydroxides and hydroxide salts with nitrate and carboxylate anions.

    PubMed

    Arizaga, Gregorio Guadalupe Carbajal; Mangrich, Antonio Salvio; Wypych, Fernando

    2008-04-01

    A layered zinc hydroxide nitrate (Zn5(OH)8(NO3)2.2H2O) and a layered double hydroxide (Zn/Al-NO3) were synthesized by coprecipitation and doped with different amounts of Cu2+ (0.2, 1, and 10 mol%), as paramagnetic probe. Although the literature reports that the nitrate ion is free (with D3h symmetry) between the layers of these two structures, the FTIR spectra of two zinc hydroxide nitrate samples show the C2v symmetry for the nitrate ion, whereas the g ||/A || value in the EPR spectra of Cu2+ is high. This fact suggests bonding of some nitrate ions to the layers of the zinc hydroxide nitrate. The zinc hydroxide nitrate was used as matrix in the intercalation reaction with benzoate, o-chlorobenzoate, and o-iodobenzoate ions. FTIR spectra confirm the ionic exchange reaction and the EPR spectroscopy reveals bonding of the organic ions to the inorganic layers of the zinc hydroxide nitrate, while the layered double hydroxides show only exchange reactions.

  17. 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.

  18. Sorption of MS2 bacteriophage to layered double hydroxides: effects of reaction time, pH, and competing anions.

    PubMed

    You, Youwen; Vance, George F; Sparks, Donald L; Zhuang, Jie; Jin, Yan

    2003-01-01

    Batch sorption and column breakthrough studies were conducted to investigate the potential of layered double hydroxides (LDHs) to remove bacteriophage MS2 from contaminated waters. All four of the LDHs evaluated in this study had very high retention capacities for MS2. Sorption results showed that MS2 could be completely removed from 5.2 x 10(2) plaque-forming units (pfu)/mL solution by Mg-Al LDH 2 (i.e., 2:1 Mg to Al ratio LDH), with the highest sorption capacity observed in this study of 1.51 x 10(10) pfu/g. Attachment of MS2 to LDHs was a rapid process and reached quasi-equilibrium after a 1-h reaction time. Within the pH range studied (pH 4-9), Mg-Al LDH 2 showed high sorption potential for MS2 at all pH values but sorption decreased slightly with increasing solution pH. Background solution anions influenced virus sorption, with SO4(2-) and HPO4(2-) decreasing sorption significantly whereas the presence of NO3- had little effect on the attachment of MS2 to Mg-Al LDH 2. The addition of another virus (phiX174) only caused a slight decrease in the retention of MS2 by Mg-Al LDH 2, suggesting that there was insignificant competitive sorption between MS2 and phiX174 on LDH surfaces. Results from column experiments indicate that there was no MS2 breakthrough from columns packed with Mg-Al LDH 2-coated sand, suggesting complete MS2 retention at the virus concentration tested. The high mass recovery by beef extract solution revealed that the removal of viruses by the LDH was due to sorption of MS2 to LDH surfaces, rather than inactivation.

  19. Layered rare-earth hydroxide nanocones with facile host composition modification and anion-exchange feature: topotactic transformation into oxide nanocones for upconversion.

    PubMed

    Zhong, Yishun; Chen, Gen; Liu, Xiaohe; Zhang, Dan; Zhang, Ning; Li, Junhui; Liang, Shuquan; Ma, Renzhi; Qiu, Guanzhou

    2017-06-22

    Conical structures with hollow interiors, namely, nanocones (NCs), may exhibit better carrier transport properties than nanorods or nanotubes, which make them promising candidates for potential applications in optical/display devices, electronics and optoelectronics. Generally, conical structures belong to a metastable state between lamellar and tubular forms due to the extreme curvature causing the increase of internal strain energy. Therefore, it is very difficult to prepare NCs in high yield and purity under mild conditions. Here we firstly demonstrate a general strategy for the synthesis of layered rare-earth hydroxide (LRH) NCs intercalating dodecyl sulfate anions (C12H25SO4(-), DS(-)) using hexamethylenetetramine (C6H12N4, HMT) hydrolysis. The rare-earth cations (RE(3+)) in the host layer can be conveniently modified and/or doped, resulting in a large family of monometallic (Y, Tb, Er), bi- (Y-Tb, Y-Er) and even tri-metallic (Y-Yb-Er) LRH NCs with adjustable ratios. Moreover, the DS(-)-intercalated LRH NCs can be readily modified with various inorganic or organic anions (e.g., NO3(-), Cl(-), and CH3COO(-), etc.) through a conventional anion-exchange procedure, and the original conical morphology can be perfectly maintained. The anion-exchanged product, for example, NO3(-)-intercalated NCs, can be more easily and topotactically transformed into oxide NCs than the original DS(-)-intercalated form, exempt from the formation of rare-earth oxysulfates induced by the combustion of interlayer DS anions. Taking advantage of this protocol, tri-metallic (Y-Yb-Er) LRH NCs were anion-exchanged into the NO3(-)-intercalated form and subsequently calcined into Y2O3:Yb,Er oxide NCs, which showed efficient upconversion photoluminescence properties. The current strategy may become a general method for the designed synthesis of other related hydroxide and oxide NCs for a wide range of potential applications.

  20. 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.

  1. Synthesis, anion exchange, and delamination of Co-Al layered double hydroxide: assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies.

    PubMed

    Liu, Zhaoping; Ma, Renzhi; Osada, Minoru; Iyi, Nobuo; Ebina, Yasuo; Takada, Kazunori; Sasaki, Takayoshi

    2006-04-12

    This paper describes a systematic study on the synthesis, anion exchange, and delamination of Co-Al layered double hydroxide (LDH), with the aim of achieving fabrication and clarifying the properties of LDH nanosheet/polyanion composite films. Co-Al-CO3 LDH hexagonal platelets of 4 mum in lateral size were synthesized by the urea method under optimized reaction conditions. The as-prepared CO3(2-)-LDH was converted to Cl- -LDH by treating with a NaCl-HCl mixed solution, retaining its high crystallinity and hexagonal platelike morphology. LDHs intercalated with a variety of anions (such as NO3-, ClO4-, acetate, lactate, dodecyl sulfate, and oleate) were further prepared from Cl- -LDH via an anion-exchange process employing corresponding salts. Exchanged products in various anion forms were found to show different delamination behaviors in formamide. Among them, best results were observed for NO3- -LDH in terms of the exfoliating degree and the quality of the exfoliated nanosheets. The delamination gave a pink transparent suspension containing well-defined nanosheets with lateral sizes of up to 2 microm. The resulting nanosheets were assembled layer-by-layer with an anionic polymer, poly(sodium styrene 4-sulfonate) (PSS), onto quartz glass substrates to produce composite films. Magnetic circular dichroism (MCD) measurements revealed that the assembled multilayer films exhibited an interesting magneto-optical response.

  2. Synthesis and adsorption properties of nanosized Mg-Al layered double hydroxides with Cl-, NO{3/-} or SO{4/2-} as interlayer anion

    NASA Astrophysics Data System (ADS)

    Hongo, T.; Wakasa, H.; Yamazaki, A.

    2011-06-01

    Nanosized Mg-Al layered double hydroxides (LDHs) with Cl-, NO{3/-} or SO{4/2-} as the interlayer anion have been synthesized by a modified coprecipitation method. The obtained LDHs were confirmed to be composed of a single phase and to be highly substituted by Al (Mg/Al ratio ˜1.9). The abilities of the LDHs to adsorb several harmful anions (F-, CrO{4/2-}, HAsO{4/2-} and HSeO3-) in aqueous solution were studied. The LDHs exhibit high adsorption abilities. The amount of adsorption onto the LDHs differed between the starting interlayer anions, and decreased in the following order of the interlayer anions: NO{3/-} > Cl- > SO{4/2-}. The NO3-formed Mg-Al LDH reached a CrO{4/2-} adsorption equilibrium state within only 30 min, much faster than those in previous reports. Thus, the nanocrystallized, highly Al substituted phase of the NO3-formed Mg-Al LDH is found to markedly enhance the anion adsorption ability.

  3. Interfacial properties of POPC/GDO liquid crystalline nanoparticles deposited on anionic and cationic silica surfaces.

    PubMed

    Chang, Debby P; Dabkowska, Aleksandra P; Campbell, Richard A; Wadsäter, Maria; Barauskas, Justas; Tiberg, Fredrik; Nylander, Tommy

    2016-09-29

    Reversed lipid liquid crystalline nanoparticles (LCNPs) of the cubic micellar (I2) phase have high potential in drug delivery applications due to their ability to encapsulate both hydrophobic and hydrophilic drug molecules. Their interactions with various interfaces, and the consequences for the particle structure and integrity, are essential considerations in their effectiveness as drug delivery vehicles. Here, we have studied LCNPs formed of equal fractions of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine and glycerol dioleate in the presence of different fractions of the stabilizer Polysorbate 80. We have used a combination of ellipsometry, quartz crystal microbalance with dissipation monitoring and neutron reflectometry to reveal the structure and composition of the adsorbed layer on both anionic silica and cationic (aminopropyltriethoxysilane) silanized surfaces. For both types of surfaces, there is a spread near-surface layer comprising lipid and polymer as well as a sparse coverage of intact particles. The composition of the near-surface layer is very close to that of the particles, in contrast to the lipid bilayer observed with related systems. The interaction is stronger for cationic than anionic surfaces, which is rationalized in terms of the negative zeta potential of the LCNPs. The work shows that the attachment of and spreading from LCNPs is influenced by the properties of the surface, the internal structure, composition and stability of the particles as well as the nature of the stabilizer.

  4. Rational design of interfacial properties of ferric (hydr)oxide nanoparticles by adsorption of fatty acids from aqueous solutions.

    PubMed

    Ponnurangam, Sathish; Chernyshova, Irina V; Somasundaran, Ponisseril

    2012-07-24

    Notwithstanding the great practical importance, still open are the questions how, why, and to what extent the size, morphology, and surface charge of metal (hydr)oxide nanoparticles (NPs) affect the adsorption form, adsorption strength, surface density, and packing order of organic (bio)molecules containing carboxylic groups. In this article, we conclusively answer these questions for a model system of ferric (hydr)oxide NPs and demonstrate applicability of the established relationships to manipulating their hydrophobicity and dispersibility. Employing in situ Fourier transform infrared (FTIR) spectroscopy and adsorption isotherm measurements, we study the interaction of 150, 38, and 9 nm hematite (α-Fe(2)O(3)) and ∼4 nm 2-line ferrihydrite with sodium laurate (dodecanoate) in water. We discover that, independent of morphology, an increase in size of the ferric (hydr)oxide NPs significantly improves their adsorption capacity and affinity toward fatty acids. This effect favors the formation of bilayers, which in turn promotes dispersibility of the larger NPs in water. At the same time, the local order in self-assembled monolayer (SAM) strongly depends on the morphological compatibility of the NP facets with the geometry-driven well-packed arrangements of the hydrocarbon chains as well as on the ratio of the chemisorbed to the physically adsorbed carboxylate groups. Surprisingly, the geometrical constraints can be removed, and adsorption capacity can be increased by negatively polarizing the NPs due to promotion of the outer-sphere complexes of the fatty acid. We interpret these findings and discuss their implications for the nanotechnological applications of surface-functionalized metal (hydr)oxide NPs.

  5. 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.

  6. New multifunctional materials obtained by the intercalation of anionic dyes into layered zinc hydroxide nitrate followed by dispersion into poly(vinyl alcohol) (PVA).

    PubMed

    Marangoni, Rafael; Ramos, Luiz Pereira; Wypych, Fernando

    2009-02-15

    Different anionic blue and orange dyes have been immobilized on a zinc hydroxide nitrate (Zn(5)(OH)(8)(NO(3))(2)nH(2)O--Zn-OH-NO(3)) by anion exchange with interlayer and/or outer surface nitrate ions of the layered matrix. Orange G (OG) was totally intercalated, orange II (OII) was partially intercalated, while Niagara blue 3B (NB) and Evans blue (EV) were only adsorbed at the outer surface. Several composite films of poly(vinyl alcohol)--PVA were prepared by casting through the dispersion of the hybrid material (Zn-OH-OG) into a PVA aqueous solution and evaporation of water in a vacuum oven. The obtained composite films were transparent, colored, and capable of absorbing UV radiation. Improved mechanical properties were also obtained in relation to the nonfilled PVA films. These results demonstrate the onset of a new range of potential applications for layered hydroxide salts in the preparation of polymer composite multifunctional materials.

  7. Abatement of aqueous anionic contaminants by thermo-responsive nanocomposites: (poly(N-isopropylacrylamide))-co-silylanized magnesium/aluminun layered double hydroxides.

    PubMed

    Chen, Hua; Qian, Guangren; Ruan, Xiuxiu; Frost, Ray L

    2015-06-15

    A series of novel thermo-responsive composite sorbents, were prepared by free-radical co-polymerization of N-isopropylacrylamide (NIPAm) and the silylanized Mg/Al layered double hydroxides (SiLDHs), named as PNIPAm-co-SiLDHs. For keeping the high affinity of Mg/Al layered double hydroxides towards anions, the layered structure of LDHs was assumed to be reserved in PNIPAm-co-SiLDHs by the silanization of the wet LDH plates as evidenced by the X-ray powder diffraction. The sorption capacity of PNIPAm-co-SiLDH (13.5 mg/g) for Orange-II from water was found to be seven times higher than that of PNIPAm (2.0mg/g), and the sorption capacities of arsenate onto PNIPAm-co-SiLDH are also greater than that onto PNIPAm, for both As(III) and As(V). These sorption results suggest that reserved LDH structure played a significant role in enhancing the sorption capacities. NO3(-) intercalated LDHs composite showed the stronger sorption capacity for Orange-II than that of CO3(2-). After sorption, the PNIPAm-co-SiLDH may be removed from water because of its gel-like nature, and may be easily regenerated contributing to the accelerated desorption of anionic contaminants from PNIPAm-co-SiLDHs by the unique phase-transfer feature through slightly heating (to 40 °C). These recyclable and regeneratable properties of thermo-responsive nanocomposites facilitate its potential application in the in-situ remediation of organic and inorganic anions from contaminated water.

  8. Synthesis of a novel layered double hydroxides [MgAl(4)(OH)(12)](Cl)(2)·2.4H(2)O and its anion-exchange properties.

    PubMed

    Chitrakar, Ramesh; Makita, Yoji; Sonoda, Akinari; Hirotsu, Takahiro

    2011-01-30

    A novel layered double hydroxide of Mg and Al with composition [Mg(0.96)Al(4.00)(OH)(12)]Cl(1.86)(CO(3))(0.03)·2.4H(2)O, designated as MgAl(4)-Cl, was synthesized by mixing crystalline gibbsite (γ-Al(OH)(3)) and solid MgCl(2)·6H(2)O with subsequent hydrothermal treatment at 160 °C for 72h. The MgAl(4)-Cl exhibited a crystalline material of a layered structure, as evidenced from X-ray diffraction. Anion uptake experiments with the MgAl(4)-Cl showed that Cl(-) in the interlayer space can be exchanged with anions such as Br(-), H(2)PO(4)(-), CO(3)(2-) or dodecyl sulfate (DS(-)) from aqueous solutions with preservation of the layered structure. Uptake of NO(3)(-), BrO(3)(-) or SO(4)(2-) on the MgAl(4)-Cl showed different behavior; these anions can be exchanged within 1h maintaining the layered structure, but a release of Mg(2+) cations from the sample was observed with increased reaction time, resulting in collapse of the layered structure and formation of the gibbsite phase, as determined from chemical analyses and X-ray diffraction. Copyright © 2010 Elsevier B.V. All rights reserved.

  9. Preparation of Mg-Al layered double hydroxide intercalated with Coomassie Brilliant Blue R anion and its uptake of aromatic compounds from aqueous solutions.

    PubMed

    Kameda, Tomohito; Sato, Syunsuke; Yoshioka, Toshiaki

    2012-01-01

    The objective of this study is to evaluate the capacity of Mg-Al layered double hydroxide (Mg-Al LDH) intercalated with organic dye to adsorb aromatic compounds in aqueous solutions. Mg-Al LDH intercalated with Coomassie Brilliant Blue R anion (BB(-)) was prepared by coprecipitation. The BB(-)-intercalated Mg-Al LDH was able to adsorb aromatic compounds from an aqueous solution, despite the electron density in the benzene ring of the aromatics. This uptake is caused by π-π stacking interactions, either between the electron-rich benzene rings of intercalated BB(-) and the benzene rings of aromatics with a low electron density or between the electron-poor benzene rings of intercalated BB(-) and the benzene rings of the aromatics with a high electron density.

  10. 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.

  11. 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.

  12. 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).

  13. 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.

  14. 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

  15. Layered double hydroxide intercalated with aromatic acid anions for the efficient capture of aniline from aqueous solution.

    PubMed

    Yu, Shujun; Wang, Xiangxue; Chen, Zhongshan; Wang, Jian; Wang, Suhua; Hayat, Tasawar; Wang, Xiangke

    2017-01-05

    Aniline is toxic and hard to be degraded, and thereby causes the environmental pollution seriously. Herein, a practical and green hydrothermal method was applied to fabricate terephthalic acid and pyromellitic acid intercalated layered double hydroxides (LDH) (named as TAL and PAL) for aniline efficient removal. The sorption of aniline on LDH-based materials were investigated at different experimental conditions, and the results indicated that aniline sorption on LDH, TAL and PAL were strongly dependent on pH and independent of ionic strength. The maximum sorption capacities of aniline on TAL and PAL at pH 5.0 and 293K were 90.4 and 130.0mg/g, respectively, which were significantly higher than that of aniline on LDH (52.6mg/g). Based on the BET, FTIR and XPS analysis, the higher sorption capacities of TAL and PAL were mainly due to high surface area and basal spacing as well as the abundant functional groups (e.g. -COO(-)). The interactions of aniline with TAL and PAL were mainly dominated by hydrogen bonds and electrostatic interactions. Such a facile synthesis method, efficient removal performance and superior reusability indicated that the aromatic acid modified LDH materials had potential application for efficient treatment of organic pollutants in environmental pollution cleanup.

  16. 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.

  17. Application of dissolvable layered double hydroxides as sorbent in dispersive solid-phase extraction and extraction by co-precipitation for the determination of aromatic acid anions.

    PubMed

    Tang, Sheng; Lee, Hian Kee

    2013-08-06

    Three types of magnesium-aluminum layered double hydroxides were synthesized and employed as solid-phase extraction (SPE) sorbents to extract several aromatic acids (protocatechuic acid, mandelic acid, phthalic acid, benzoic acid, and salicylic acid) from aqueous samples. An interesting feature of these sorbents is that they dissolve when the pH of the solution is lower than 4. Thus, the analyte elution step, as needed in conventional sorbent-based extraction, was obviated by dissolving the sorbent in acid after extraction and separation from the sample solution. The extract was then directly injected into a high-performance liquid chromatography-ultraviolet detection system for analysis. In the key adsorption process, both dispersive SPE and co-precipitation extraction with the sorbents were conducted and experimental parameters such as pH, temperature, and extraction time were optimized. The results showed that both extraction methods provided low limits of detection (0.03-1.47 μg/L) and good linearity (r(2) > 0.9903). The optimized extraction conditions were applied to human urine and sports drink samples. This new and interesting extraction approach was demonstrated to be a fast and efficient procedure for the extraction of organic anions from aqueous samples.

  18. Investigation of gamma radiation effect on the anion exchange resin Amberlite IRA-400 in hydroxide form by Fourier transformed infrared and 13C nuclear magnetic resonance spectroscopies.

    PubMed

    Traboulsi, A; Dupuy, N; Rebufa, C; Sergent, M; Labed, V

    2012-03-02

    Radiation-induced decomposition of the anion exchange resin Amberlite IRA-400 in hydroxide form by gamma radiolysis has been studied under different irradiation doses and irradiation atmospheres. In this work, we focused on the degradation of the solid part of the resin by Fourier transformed infrared (FTIR) and (13)C nuclear magnetic resonance (NMR) spectroscopies associated with chemometric treatments. FTIR and (13)C NMR techniques showed that only -CH(2)N(+)(CH(3))(3) groups were detached from the resin whereas the polystyrene divinylbenzene backbone remains intact. The quaternary ammonium groups were replaced by amine or carbonyl groups according to the irradiation atmosphere (with or without water or oxygen). Principal components analysis (PCA) was used to classify the degraded resins according to their irradiation conditions by separating the effect of the dose or the environment. The PCA loadings have shown spectral regions which discriminate the irradiated resins whereas SIMPLe-to-use Interactive Self-modeling Mixture Analysis (SIMPLISMA) allows to identify families of component characterizing the chemical structure of resins and estimate their relative contributions according to the irradiation atmospheres.

  19. Preparation of an anionic azo pigment-pillared layered double hydroxide and the thermo- and photostability of the resulting intercalated material

    NASA Astrophysics Data System (ADS)

    Guo, Shengchang; Li, Dianqing; Zhang, Weifeng; Pu, Min; Evans, David G.; Duan, Xue

    2004-12-01

    A large anionic pigment has been intercalated into a layered double hydroxide (LDH) host by ion-exchange of an Mg/Al LDH-nitrate precursor with a solution of C.I. Pigment Red 48:2 (the calcium salt of 4-((5-chloro-4-methyl-2-sulfophenyl)azo)-3-hydroxy-2-naphthalene-carboxylic acid), in ethane-1,2-diol. After intercalation of the pigment, the interlayer distance in the LDH increases from 0.86 to 1.72 nm. Infrared spectra and TG-DTA curves reveal the presence of a complex system of supramolecular host-guest interactions. The UV-visible diffuse reflectance spectra of C.I. Pigment Red 48:2 show marked changes after heating at 200 °C and above, whereas there are no significant changes in the spectra of the intercalated pigment after heating at temperatures up to 300 °C, showing that the thermostability is markedly enhanced by intercalation in the LDH host. The pigment-intercalated LDHs exhibits much higher photostability to UV light than the pristine pigment, in the case of both the pure solids and their composites with polypropylene, as shown by measurement of CIE 1976 L*a*b* color difference ( ΔE) values.

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

    SciTech Connect

    Paradies, Henrich H. E-mail: hparadies@jacobs-university.de; Reichelt, Hendrik

    2016-06-15

    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.

  1. 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.

  2. Engineering interfacial properties by anionic surfactant-chitosan complexes to improve stability of oil-in-water emulsions.

    PubMed

    Zinoviadou, Kyriaki G; Scholten, Elke; Moschakis, Thomas; Biliaderis, Costas G

    2012-03-01

    Oil-in-water emulsions (10% w/w n-tetradecane) were prepared at pH = 5.7 by using, as surface active agents, electrostatically formed complexes of sodium stearoyl lactylate (SSL) at a concentration of 0.4% (w/w) and chitosan (CH) in a concentration range between 0 and 0.48% w/w. The use of complexes in emulsions with a low concentration of CH (<0.24% w/w) resulted in highly flocculated systems; instead, with increased level of CH, the emulsions had a smaller average droplet size and exhibited greater stability during storage. Emulsions stabilised by SSL/CH complexes showed non-Newtonian flow behavior with pronounced shear thinning. Among all formulations studied none showed a gel-like behavior since in all cases the G' (storage modulus) was lower that G'' (loss modulus). Adsorption kinetics of pure SSL and SSL/CH complexes to the oil/water interfaces were evaluated using an automated drop tensiometer (ADT). Even though complexation of SSL with CH resulted in a delay of the adsorption of the surface active species at the oil/water interface, the inclusion of the polysaccharide resulted in substantially improved interfacial properties as indicated by a significant increase of the dilatational modulus. Furthermore, the enhanced interfacial properties of the emulsion droplets resulted in improved stability against freeze-thaw cycling. The results of this study may facilitate the development of frozen food products such as desserts with an ameliorated stability and favorable sensorial characteristics.

  3. 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 ...

  4. 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.

  5. Synthesis, sustained release properties of magnetically functionalized organic-inorganic materials: Amoxicillin anions intercalated magnetic layered double hydroxides via calcined precursors at room temperature

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Liu, Qi; Zhang, Guangchun; Li, Zhanshuang; Yang, Piaoping; Jing, Xiaoyan; Zhang, Milin; Liu, Tianfu; Jiang, Zhaohua

    2009-09-01

    Zinc-aluminum-carbonate-layered double hydroxides (ZnAl-CO 3-LDHs), loaded with magnetic substrates (Fe 3O 4), were prepared for sustained drug-targeting delivery. From the X-ray diffraction results, it was found that the magnetic substrates were successfully incorporated with LDHs and highly dispersed in the hydrotalcite structure. After intercalation with an antibiotic drug (amoxicillin) by using a calcinations-reconstruction method, the basal spacing of layered double hydroxides increased from 7.51 Å to 12.35 Å, indicating that amoxicillin was successfully intercalated into the interlay space of LDHs as a monolayer. Furthermore, in vitro drug release experiments in pH 7.4 phosphate buffer solution (PBS) showed sustained release profiles with amoxicillin as a model drug. Magnetic measurements revealed that the composite possessed paramagnetic properties at room temperature.

  6. 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.

  7. 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.

  8. 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

    2011-11-03

    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.

  9. Evidence of Multiple Sorption Modes in Layered Double Hydroxides Using Mo As Structural Probe.

    PubMed

    Ma, Bin; Fernandez-Martinez, Alejandro; Grangeon, Sylvain; Tournassat, Christophe; Findling, Nathaniel; Claret, Francis; Koishi, Ayumi; Marty, Nicolas C M; Tisserand, Delphine; Bureau, Sarah; Salas-Colera, Eduardo; Elkaïm, Erik; Marini, Carlo; Charlet, Laurent

    2017-05-16

    Layered double hydroxides (LDHs) have been considered as effective phases for the remediation of aquatic environments, to remove anionic contaminants mainly through anion exchange mechanisms. Here, a combination of batch isotherm experiments and X-ray techniques was used to examine molybdate (MoO4(2-)) sorption mechanisms on CaAl LDHs with increasing loadings of molybdate. Advanced modeling of aqueous data shows that the sorption isotherm can be interpreted by three retention mechanisms, including two types of edge sites complexes, interlayer anion exchange, and CaMoO4 precipitation. Meanwhile, Mo geometry evolves from tetrahedral to octahedral on the edge, and back to tetrahedral coordination at higher Mo loadings, indicated by Mo K-edge X-ray absorption spectra. Moreover, an anion exchange process on both CaAl LDHs was followed by in situ time-resolved synchrotron-based X-ray diffraction, remarkably agreeing with the sorption isotherm. This detailed molecular view shows that different uptake mechanisms-edge sorption, interfacial dissolution-reprecipitation-are at play and control anion uptake under environmentally relevant conditions, which is contrast to the classical view of anion exchange as the primary retention mechanism. This work puts all these mechanisms in perspective, offering a new insight into the complex interplay of anion uptake mechanisms by LDH phases, by using changes in Mo geometry as powerful molecular-scale probe.

  10. Polysulfide intercalated layered double hydroxides for metal capture applications

    DOEpatents

    Kanatzidis, Mercouri G.; Ma, Shulan

    2017-04-04

    Polysulfide intercalated layered double hydroxides and methods for their use in vapor and liquid-phase metal capture applications are provided. The layered double hydroxides comprise a plurality of positively charged host layers of mixed metal hydroxides separated by interlayer spaces. Polysulfide anions are intercalated in the interlayer spaces.

  11. Studies of Oxide Anions

    DTIC Science & Technology

    1991-06-01

    oxide and metal hydroxide anions and related clusters of species including ones comprised of tungsten, tantalum , molybdenum and niobium . After...molybdenum, tantalum and niobium were produced. For the case of molybdenum, we observed oxides from MoO3 - to Mo3Of-, for tantalum , TaO4 - to Ta5O 16- and...of Nb. Analogous to the niobium case, all three tantalum oxide anions lead to the same four sequential products. The results show that whenever there

  12. 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.

  13. 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.

  14. 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.

  15. Sodium hydroxide poisoning

    MedlinePlus

    Sodium hydroxide is a very strong chemical. It is also known as lye and caustic soda. This ... poisoning from touching, breathing in (inhaling), or swallowing sodium hydroxide. This article is for information only. Do ...

  16. Hydroxide ion hydration in aqueous solutions.

    PubMed

    Smiechowski, Maciej; Stangret, Janusz

    2007-04-19

    Hydroxide ion hydration was studied in aqueous solutions of selected alkali metal hydroxides by means of Fourier transform infrared (FTIR) spectroscopy of HDO isotopically diluted in H2O. The quantitative difference spectra procedure was applied for the first time to investigate such systems. It allowed removal of bulk water contribution and separation of the spectra of solute-affected HDO. The obtained spectral data were confronted with ab initio calculated structures of small gas-phase and polarizable continuum solvation model (PCM) solvated aqueous clusters, OH-(H2O)n, n = 1-7, to establish the structural and energetic states of hydration spheres of the hydrated hydroxide anion. This was achieved by comparison of the calculated optimal geometries with the interatomic distances derived from HDO band positions. The energetic state of water in OH- hydration shells, as revealed by solute-affected HDO spectra, is similar to that of an isoelectronic F- anion. No evidence was found for the existence of stable hydroxide dimer, H3O2-, in an aqueous solution. Spectral data do confirm, however, existence of a weak interaction with a single water molecule at the hydrogen site of OH-.

  17. Tunable electronic interactions between anions and perylenediimide.

    PubMed

    Goodson, Flynt S; Panda, Dillip K; Ray, Shuvasree; Mitra, Atanu; Guha, Samit; Saha, Sourav

    2013-08-07

    Over the past decade anion-π interaction has emerged as a new paradigm of supramolecular chemistry of anions. Taking advantage of the electronic nature of anion-π interaction, we have expanded its boundaries to charge-transfer (CT) and formal electron transfer (ET) events by adjusting the electron-donating and accepting abilities of anions and π-acids, respectively. To establish that ET, CT, and anion-π interactions could take place between different anions and π-acids as long as their electronic and structural properties are conducive, herein, we introduce 3,4,9,10-perylenediimide (PDI-1) that selectively undergoes thermal ET from strong Lewis basic hydroxide and fluoride anions, but remains electronically and optically silent to poor Lewis basic anions, as ET and CT events are turned OFF. These interactions have been fully characterized by UV/Vis, NMR, and EPR spectroscopies. These results demonstrate the generality of anion-induced ET events in aprotic solvents and further refute a notion that strong Lewis basic hydroxide and fluoride ions can only trigger nucleophilic attack to form covalent bonds instead of acting as sacrificial electron donors to π-acids under appropriate conditions.

  18. Calcium hydroxide poisoning

    MedlinePlus

    These products contain calcium hydroxide: Cement Limewater Many industrial solvents and cleaners (hundreds to thousands of construction products, flooring strippers, brick cleaners, cement thickening products, and many ...

  19. Trifluoromethylsulfonyl derivatives of benzofuroxane and their anionic sigma-complexes

    SciTech Connect

    Yagupol'skii, L.M.; Gogoman, I.V.; Shchupak, G.M.; Boiko, V.N.

    1986-09-10

    Syntheses are reported for 4-nitro-6-trifluoromethylsulfonyl- and 4,6-bis(trifluoromethylsulfonyl)benzofuroxanes and their anionic sigma-complexes with hydroxide and methylate anions. In contrast to its 4,6-dinitro analog, 4,6-bis(trifluoromethylsulfonyl)benzofuroxane forms stable sigma-complexes with sodium acetate and sodium azide and has higher acidity by an order of magnitude.

  20. 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.

  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. A Highly Hydroxide Conductive, chemically Stable Anion Exchange Membrane, Poly(2,6 dimethyl 1,4 phenylene oxide)-b-Poly(vinyl benzyl trimethyl ammonium), for Electrochemical Applications

    SciTech Connect

    Pandey, Tara P.; Sarode, Himanshu N.; Yang, Yating; Yang, Yuan; Vezzu, Keti; Di Noto, Vito; Seifert, Soenke; Knauss, Daniel M.; Liberatore, Matthew W.; Herring, Andrew M

    2016-01-01

    A chemically stable copolymer [poly(2,6 dimethyl 1,4 phenylene oxide)-b-poly(vinyl benzyl trimethyl ammonium)] with two ion exchange capacities, 3.2 and 2.9 meq g−1, was prepared as anion exchange membranes (AEM-3.2 and AEM-2.9). These materials showed high OH− conductivities of 138 mS.cm−1 and 106 mS.cm−1, for AEM-3.2 and AEM-2.9 respectively, at 60°C, and 95% RH. The OH− conductivity = 45 mS.cm−1 for AEM-3.2 at 60% RH and 60°C in the absence of CO2. Amongst the ions studied, only OH− is fully dissociated at high RH. The lower Ea = 10–13 kJ.mol−1 for OH− compared to F− ∼ 20 kJ.mol−1 in conductivity measurements, and of H2O from self-diffusion coefficients suggests the presence of a Grotthuss hopping transport mechanism in OH− transport. PGSE-NMR of H2O and F− show that the membranes have low tortuosity, 1.8 and 1.2, and high water self-diffusion coefficients, 0.66 and 0.26 × 10−5 cm2.s−1, for AEM-3.2 and AEM-2.9 respectively. SAXS and TEM show that the membrane has several different sized water environments, ca. 62 nm, 20 nm, and 3.5 nm. The low water uptake, λ = 9–12, reduced swelling, and high OH− conductivity, with no chemical degradation over two weeks, suggests that the membrane is a strong candidate for electrochemical applications.

  3. 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

    2015-04-07

    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.

  4. Anion-incorporation model proposed for interpreting the interfacial physical origin of the faradaic pseudocapacitance observed on anodized valve metals--with anodized titanium in fluoride-containing perchloric acid as an example.

    PubMed

    Kong, De-Sheng

    2010-04-06

    With anodized titanium in fluoride-containing perchloric acid solution as an example in the present Article, the physical origin of the faradaic pseudocapacitance C(0) frequently observed in electrochemical impedance spectroscopy (EIS) spectra at low frequencies was interpreted for the first time by the incorporation/insertion of some electrolyte anions (i.e., F(-)-ions in this work) into the oxide film under the electric field during film growth. It was shown that the emergence of the faradaic pseudocapacitive behavior not only indicates a significant incorporation of anions into the oxide films but also reflects the arrival of them at the metal/oxide interface. The anion incorporation/transfer process was depicted with a modified point-defect model and simulated by a blocking, restricted finite-length diffusion impedance model (which has been widely used for studying the ion-insertion electrodes). The fast inward migration of the incorporated electrolyte species, along with the accumulation of them at the metal/film interface (due to the blocking effect of this interface), is responsible for the low-frequency capacitance behavior revealed by a vertical capacitive line in EIS spectra at low frequencies for anodically growing oxide films on valve metals. Many related published results for anodized valve metals (such as Ti, Bi, Ta, Al, etc.) are in good accordance with the model predictions. This work also suggests that the electrochemical method for the preparation of F(-)-doped TiO(2) thin film materials should be an easy, low-cost, and even more effective one to be used.

  5. 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.

  6. Mixed-valence hydroxides as bioorganic host minerals

    NASA Technical Reports Server (NTRS)

    Kuma, K.; Paplawsky, W.; Gedulin, B.; Arrhenius, G.

    1989-01-01

    A range of naturally occurring divalent-trivalent metal cation hydroxides and modified artifical analogs have been synthesized and characterized. Structural and chemical properties of these minerals, determining their capability to selectively concentrate, order and alter molecules of prebiotic interest, include their anion exchange capacity and specificity, photochemical reactivity, production of nascent hydrogen, and catalytic efficiency. Properties relevant to these functions have been investigated and are discussed.

  7. 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.

  8. Interfacial effects in multilayers

    SciTech Connect

    Barbee, T.W., Jr.

    1998-04-01

    Interfacial structure and the atomic interactions between atoms at interfaces in multilayers or nano-laminates have significant impact on the physical properties of these materials. A technique for the experimental evaluation of interfacial structure and interfacial structure effects is presented and compared to experiment. In this paper the impact of interfacial structure on the performance of x-ray, soft x-ray and extreme ultra-violet multilayer optic structures is emphasized. The paper is concluded with summary of these results and an assessment of their implications relative to multilayer development and the study of buried interfaces in solids in general.

  9. 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.

  10. Chemical modification of zinc hydroxide nitrate and Zn-Al-layered double hydroxide with dicarboxylic acids.

    PubMed

    Arizaga, Gregorio Guadalupe Carbajal; Mangrich, Antonio Salvio; da Costa Gardolinski, José Eduardo Ferreira; Wypych, Fernando

    2008-04-01

    A zinc hydroxide nitrate (ZHN), Zn5(OH)8(NO3)2.2H2O, and a layered double hydroxide (LDH), Zn/Al-NO3 were doped with 0.2 mol% of Cu2+ during alkaline chemical precipitation. Both compounds were intercalated with adipate ((-)OOC(CH2)4COO(-)), azelate ((-)OOC(CH2)7COO(-)), and benzoate (C6H5COO(-)) ions through ion exchange reactions. Solid state 13C nuclear magnetic resonance spectroscopy showed only one signal of carboxylic carbon for adipate and azelate intercalated into LDH, indicating that the carboxylic ends of both acids were equivalent, whereas the signal split when the intercalation was into the ZHN matrix. The electron paramagnetic resonance (EPR) spectrum of copper in octahedral cation sites of LDH layers showed a Hamiltonian parameter ratio g ||/A ||=170 cm and, after intercalation of adipate, the change was not significant: g ||/A ||=174 cm. This result indicates that the carboxylate ions did not coordinate with copper centers. Nonetheless, the intercalation of azelate increased the ratio to g ||/A ||=194 cm, similar to the spectra of ZHN modified with adipate, g ||/A ||=199 cm, and azelate, g ||/A ||=183 and 190 cm, which are associated with the coordination of copper by weak carboxylate anion ligands. Copper occupies octahedral or tetrahedral sites in ZHN layers, and the EPR spectra indicate that the dicarboxylate anions reacted preferentially with octahedral sites, whereas benzoate reacted with both sites.

  11. Novel synthesis of layered double hydroxides (LDHs) from zinc hydroxide

    NASA Astrophysics Data System (ADS)

    Meng, Zilin; Zhang, Yihe; Zhang, Qian; Chen, Xue; Liu, Leipeng; Komarneni, Sridhar; Lv, Fengzhu

    2017-02-01

    The most common synthesis methods for layered double hydroxides (LDHs) are co-precipitation and reconstruction, which can have some limitations for application. Here, we report a novel synthesis method for LDHs. We use zinc hydroxide as the precursor to synthesize LDHs phase through a simple transformation process of zinc hydroxide phase. For this transformation process, aluminum can enter into zinc hydroxide and replace zinc quickly to transform it into LDH by creating positive charges in the zinc hydroxide solid phase. The mechanism of LDH formation was through Al3+ reaction first with zinc hydroxide followed by recrystallization of the original structure of zinc hydroxide. Thus, the new process of LDH formation involves a reaction of Al to substitute for Zn and recrystallization leading to LDH and the final pH influences the crystallization of LDHs by this process. In addition, Cr3+ was employed as a trivalent cation for LDH formation to react with zinc hydroxide, which also led to LDH structure.

  12. 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.

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

    PubMed

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

    2016-05-06

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

  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.

  15. 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 the...

  16. 21 CFR 184.1631 - Potassium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Potassium hydroxide. 184.1631 Section 184.1631... GRAS § 184.1631 Potassium hydroxide. (a) Potassium hydroxide (KOH, CAS Reg. No. 1310-58-3) is also... powders. Potassium hydroxide is obtained commercially from the electrolysis of potassium chloride solution...

  17. 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 the...

  18. 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 the...

  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 the...

  20. Cobalt improves nickel hydroxide electrodes for batteries

    NASA Technical Reports Server (NTRS)

    Lerner, S. R.; Seiger, H. N.

    1969-01-01

    Positive nickel hydroxide electrodes containing 20 mole percent of cobalt hydroxide are more efficient than when impregnated to the same degree by weight with nickel hydroxide alone. Charge-acceptance and oxygen-evolution tests indicate cobalt electrodes are more efficient than plain positive nickel hydroxide electrodes at all rates of charge.

  1. 21 CFR 184.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Magnesium hydroxide. 184.1428 Section 184.1428... Listing of Specific Substances Affirmed as GRAS § 184.1428 Magnesium hydroxide. (a) Magnesium hydroxide... is prepared as a white precipitate by the addition of sodium hydroxide to a water soluble magnesium...

  2. 21 CFR 184.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Magnesium hydroxide. 184.1428 Section 184.1428... Listing of Specific Substances Affirmed as GRAS § 184.1428 Magnesium hydroxide. (a) Magnesium hydroxide... is prepared as a white precipitate by the addition of sodium hydroxide to a water soluble magnesium...

  3. Superior coagulation of graphene oxides on nanoscale layered double hydroxides and layered double oxides.

    PubMed

    Zou, Yidong; Wang, Xiangxue; Chen, Zhongshan; Yao, Wen; Ai, Yuejie; Liu, Yunhai; Hayat, Tasawar; Alsaedi, Ahmed; Alharbi, Njud S; Wang, Xiangke

    2016-12-01

    With the development and application of graphene oxides (GO), the potential toxicity and environmental behavior of GO has become one of the most forefront environmental problems. Herein, a novel nanoscale layered double hydroxides (glycerinum-modified nanocrystallined Mg/Al layered double hydroxides, LDH-Gl), layered double oxides (calcined LDH-Gl, LDO-Gl) and metallic oxide (TiO2) were synthesized and applied as superior coagulants for the efficient removal of GO from aqueous solutions. Coagulation of GO as a function of coagulant contents, pH, ionic strength, GO contents, temperature and co-existing ions were studied and compared, and the results showed that the maximum coagulation capacities of GO were LDO-Gl (448.3 mg g(-1)) > TiO2 (365.7 mg g(-1)) > LDH-Gl (339.1 mg g(-1)) at pH 5.5, which were significantly higher than those of bentonite, Al2O3, CaCl2 or other natural materials due to their stronger reaction active and interfacial effect. The presence of SO3(2-) and HCO3(-) inhibited the coagulation of GO on LDH-Gl and LDO-Gl significantly, while other cations (K(+), Mg(2+), Ca(2+), Ni(2+), Al(3+)) or anion (Cl(-)) had slightly effect on GO coagulation. The interaction mechanism of GO coagulation on LDO-Gl and TiO2 might due to the electrostatic interactions and strong surface complexation, while the main driving force of GO coagulation on LDH-Gl might be attributed to electrostatic interaction and hydrogen bond, which were further evidenced by TEM, SEM, FT-IR and XRD analysis. The results of natural environmental simulation showed that LDO-Gl, TiO2 or other kinds of natural metallic oxides could be superior coagulants for the efficient elimination of GO or other toxic nanomaterials from aqueous solutions in real environmental pollution cleanup.

  4. Hydroxide catalysts for lignin depolymerization

    DOEpatents

    Beckham, Gregg T.; Biddy, Mary J.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-04-25

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

  5. 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.

  6. 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.

  7. Cellular Uptake Behavior of Fluorescein: Intercalated Layered Double Hydroxide

    NASA Astrophysics Data System (ADS)

    Tanaka, Miyuki; Aisawa, Sumio; Hirahara, Hidetoshi; Narita, Eiichi; Yin, Shu; Sato, Tsugio

    2012-06-01

    In order to define the ability of layered double hydroxide (LDH) as materials for drug delivery, fluorescein (Fluo) anion intercalated LDH (Fluo/LDH) was synthesized by hydrothermal treatment and observed the cellular uptake of the Fluo/LDH for mammalian cell (L929). The synthesized Fluo/LDH showed a LDH structure, high fluorescence and low cytotoxicity. According to the fluorescence, confocal and TEM images of cells, the Fluo/LDH seemed to be internalized into the L929 cell by cellular endocytosis and dissolved inside the cell to exhibit the fluorescence of cellular cytoplasm.

  8. Anion Gap Blood Test

    MedlinePlus

    ... Why do I need an anion gap blood test? Your health care provider may have ordered an anion gap blood ... which is a blood test. During a blood test, a health care professional uses a small needle to take a ...

  9. 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.

  10. 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.

  11. Anions in Cometary Comae

    NASA Technical Reports Server (NTRS)

    Charnley, Steven B.

    2011-01-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

  12. Sorption of phosphate and Cr(VI) by Fe(III) and Cr(III) hydroxides.

    PubMed

    Tzou, Y M; Wang, M K; Loeppert, R H

    2003-05-01

    Understanding the chemical behavior and interactions of Cr(VI) ( e.g., HCrO(4)(-)) and other anions, such as orthophosphate (P) with insoluble metal hydroxides ( i.e., Cr[III] and Fe[III]) in disposal landfills or in chromite ore processing residue (CORP)-enriched soil is very important in predicting the movement and the fate of Cr(VI). This study evaluates the sorption behavior of P and Cr(VI) by Fe(III) ( i.e., ferrihydrite), Cr(III) ( i.e., Cr[OH](3)), and coprecipitated Fe(III)/Cr(III) hydroxides. These metal hydroxide sorbents were synthesized, and sorption of P and Cr(VI) were conducted at different pH using a batch technology. Our results show that P and Cr(VI) sorption by metal hydroxides decreased with increasing suspension pH. Greater decrease in P sorption was observed when Cr(III) was present in the structures of hydroxides. Following the sorption of low concentration of P ( i.e., 0.5 mM), the sorption of subsequently added Cr(VI) by hydroxides was less influenced. However, Cr(VI) sorption was greatly inhibited when high concentration of P ( i.e., 10 mM) prereacted with hydroxides, particularly in Fe(III) hydroxide system. Results also indicated that high concentration of Cr(VI) (10 mM) could dissolve Cr(III) hydroxide at pH 3 and reprecipitate as an amorphous form of Cr(VI) and Cr(III) compound at pH about 6.5. Although coprecipitation of Cr(VI) with Cr(III) can inhibit Cr(VI) movement through soil profiles, the inhibition seems to be low due to the gradual release of Cr(VI) with increasing pH.

  13. Interfacial bonding stability

    NASA Technical Reports Server (NTRS)

    Boerio, J.

    1984-01-01

    Interfacial bonding stability by in situ ellipsometry was investigated. It is found that: (1) gamma MPS is an effective primer for bonding ethylene vinyl acetate (EVA) to aluminum; (2) ellipsometry is an effective in situ technique for monitoring the stability of polymer/metal interfaces; (3) the aluminized back surface of silicon wafers contain significant amounts of silicon and may have glass like properties.

  14. 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.

  15. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

    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.

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

    PubMed

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

    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.

  18. Modulation of organic interfacial spin polarization by interfacial angle

    NASA Astrophysics Data System (ADS)

    Zhang, Zhao; Li, Ying; Zhang, Guang-ping; Ren, Jun-feng; Wang, Chuan-kui; Hu, Gui-chao

    2017-01-01

    Based on ab initio theory, we theoretically investigated the interfacial spin polarization by adsorbing a benzene-dithiolate molecule onto a nickel surface with different interfacial angles. A variable magnitude and even an inversion of the interfacial spin polarization are observed with the increase of the interfacial angle. The orbital analysis shows that the interfacial spin polarization is codetermined by two kinds of orbital hybridization between the molecule and the ferromagnet, the pz-d hybridization and the sp3-d hybridization, which show different dependence on the angle. These results indicate a new way to manipulate the spin polarization at organic spinterface.

  19. Enhanced sequestration of Cr(VI) by nanoscale zero-valent iron supported on layered double hydroxide by batch and XAFS study.

    PubMed

    Sheng, Guodong; Hu, Jun; Li, Hui; Li, Jiaxing; Huang, Yuying

    2016-04-01

    Herein, the reduction of nanoscale zero-valent iron (NZVI) and adsorption of layered double hydroxides (LDH) to sequester Cr(VI) were well combined by the immobilization of NZVI onto LDH surface (NZVI/LDH). The characterization results revealed that LDH decreased NZVI aggregation and thus increased Cr(VI) sequestration. The batch results indicated that Cr(VI) sequestration by NZVI/LDH was higher than that of NZVI, and superior to the sum of reduction and adsorption. The LDH with good anion exchange property allowed the adsorption of Cr(VI), facilitating interfacial reaction by increasing the local concentration of Cr(VI) in the NZVI vicinity. X-ray absorption near edge structure (XANES) results indicated that Cr(VI) was almost completely reduced to Cr(III) by NZVI/LDH, but Cr(VI) was partly reduced to Cr(III) by NZVI with a trace of Cr(VI) adsorbed on corrosion products. The coordination environment of Cr from extended X-ray absorption fine structure (EXAFS) analysis revealed that LDH could be a good scavenger for the insoluble products produced during reaction. So, the insoluble products on NZVI could be reduced, and its reactivity could be maintained. These results demonstrated that NZVI/LDH exhibits multiple functionalities relevant to the remediation of Cr(VI)-contaminated sites.

  20. Preparation and characterization of lactate-intercalated Co-Fe layered double hydroxides and exfoliated nanosheet film with low infrared emissivity

    NASA Astrophysics Data System (ADS)

    Zhu, Yunxia; Zhou, Yuming; Zhang, Tao; He, Man; Wang, Yongjuan; Yang, Xiaoming; Yang, Yong

    2012-12-01

    Lactate-intercalated Co-Fe layered double hydroxides (LDHs) were successfully prepared by coprecipitation and hydrothermal method. In this process, divalent metal ions as precursors can be obtained from the reduction reaction of lactic acid and metal powder (cobalt and ferrous). In order to obtain Fe3+, H2O2 (30%) was used to oxidize Fe2+. Meanwhile, the produced lactate was intercalated into the LDHs interlayers to compensate the positively charged layers. The as-synthesized LDHs were studied by element chemical analysis, powder X-ray diffraction (XRD), FT-IR spectroscopy, thermogravitry (TG) and differential scanning calorimetry (DSC), TEM. The results indicated that the basal spacing value of the LDHs was larger than that of lactate-intercalated Mg-Al or Zn-Al LDHs. It proved that the lactate anions were inserted into the gallery in the form of dimers which made it easy to be delaminated in water. The obtained nanosheets were deposited on the substrates to form the film which was characterized by TEM and AFM, and infrared emissivity value (8-14 μm) was also investigated. The infrared emissivity values of Co-Fe LDHs were lower than that of Zn-Al which took advantage of the special electronic structure in Co and Fe. Besides, the orderly structure and the reduction of the interfacial deficiency of the film made the values further reduced.

  1. 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 feeding...

  2. 21 CFR 582.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Additives § 582.1763 Sodium hydroxide. (a) Product. Sodium hydroxide. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or feeding practice. ...

  3. 21 CFR 582.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Additives § 582.1205 Calcium hydroxide. (a) Product. Calcium hydroxide. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or feeding...

  4. 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.

  5. Removal of fluoride from water using iron oxide-hydroxide nanoparticles.

    PubMed

    Raul, Prasanta Kumar; Devi, Rashmi Rekha; Umlong, Iohborlang M; Banerjee, Saumen; Singh, Lokendra; Purkait, Mihir

    2012-05-01

    A novel and facile method for the synthesis of uniform stoichiometric powder form of non-magnetic iron oxide-hydroxide nanoparticles with spherical morphology and its application for defluoridation of drinking water is reported. X-ray powder diffraction analysis (XRD), BET surface area, FTIR, field emission scanning electron microscopy (FESEM) and Transmission electron microscopy (TEM) images were used to characterize nanoscale iron oxide-hydroxide. Transmission electron microscopy (TEM) image revealed the formation of iron oxide-hydroxide nanoparticles with spherical morphology. The iron oxide-hydroxide nanoparticles showed an excellent ability to remove fluoride (F-) from contaminated water over a wide range of pH. The influences of temperature, stirring speed, pH, adsorbent dose and contact time were studied. The equilibrium data were tested with various isotherm models and finally, a calculation procedure was reported for the calculation of adsorbent requirement. The fluoride adsorbed nanoparticles was regenerated upto 70% using sodium hydroxide or hydrochloric acid solution. The iron oxide-hydroxide nanoparticles can be used as an effective and replicable adsorbent media for defluoridation of water in presence of competing anions like chloride, iodate, iodide and sulphate.

  6. 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.

  7. 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.

  8. Adsorption of hydrated hydroxide and hydronium ions on Ag(1 1 1). A quantum mechanical investigation

    NASA Astrophysics Data System (ADS)

    Patrito, E. M.; Paredes-Olivera, P.

    2003-03-01

    In this paper we have studied comparatively the adsorption of hydroxide and hydronium ions, extending our previous study on hydronium adsorption [J. Phys. Chem. B. 105 (2001) 7227] and emphasizing the adsorption of hydroxide. The calculations were performed on the 111 surface of silver using ab initio quantum mechanical methods (Hartree-Fock+Moller-Plesset second order perturbation theory). The adsorption was investigated for the bare and the hydrated ions (up to three water molecules). Binding energies, equilibrium structures and charge transfer processes were investigated. While the successive hydration of hydronium detaches the ion from the surface, the hydrated hydroxide anion remains specifically adsorbed. Charge transfer processes between the adsorbates and the surface were studied using electron density difference plots and effective charges obtained from Mulliken populations and from surface-dipole moment curves. The energetics of the surface reactions leading to the formation of the hydrated hydronium and hydroxide ions from the bare adsorbed ions and water molecules was also investigated. Both reactions are exothermic mainly due to the formation of strong hydrogen bonds. The effect of an external homogeneous electric field perpendicular to the surface on different adsorbate properties was investigated for the bare and hydrated hydroxide ion in order to model the environment of the electrical double layer. The electric field affects the orientation of the water molecules on the surface and the hydroxide surface distance.

  9. 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. This...

  10. 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. This...

  11. 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. This...

  12. 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. This...

  13. 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. This...

  14. 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. This...

  15. 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. This...

  16. 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. This...

  17. 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. This...

  18. 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. This...

  19. 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...

  20. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium hydroxide. 184.1763 Section 184.1763 Food... Specific Substances Affirmed as 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....

  1. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium hydroxide. 184.1763 Section 184.1763 Food... Specific Substances Affirmed as 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....

  2. 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...

  3. 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...

  4. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium hydroxide. 184.1763 Section 184.1763 Food... Specific Substances Affirmed as 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....

  5. 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...

  6. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium hydroxide. 184.1763 Section 184.1763 Food... Specific Substances Affirmed as 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....

  7. Contribution to the knowledge of nickel hydroxide electrodes. 5. Analysis and electrochemical behavior of cadmium nickel hydroxides

    NASA Technical Reports Server (NTRS)

    Bode, H.; Dennstedt, W.

    1981-01-01

    Electrochemical experiments performed at sintered and bulk electrodes show that beta nickel hydroxide contains an electrochemically inactive proportion of cadmium hydroxide of up to 10%. The electrochemically ineffective cadmium hydroxide is homogeneously dissolved in beta nickel hydroxide.

  8. 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.

  9. Infared Spectroscopy of Discrete Uranyl Anion Complexes

    SciTech Connect

    Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Kullman, Michael; Moore, David T.; Polfer, Nick; Oomens, Jos; Infante, Ivan A.; Visscher, Lucas; Siboulet, Bertrand; De Jong, Wibe A.

    2008-01-24

    The Free-Electron Laser for Infrared Experiments (FELIX) w 1 as used to study the wavelength-resolved multiple photon photodissociation of discrete, gas phase uranyl (UO2 2 2+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations predicted values that were 30–40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity.

  10. Surfactant behavior of "ellipsoidal" dicarbollide anions: a molecular dynamics study.

    PubMed

    Chevrot, G; Schurhammer, R; Wipff, G

    2006-05-18

    We report a molecular dynamics study of cobalt bis(dicarbollide) anions [(B(9)C(2)H(8)X(3))(2)Co](-) (XCD(-)) commonly used in liquid-liquid extraction (X = H, Me, Cl, or Br), showing that these anions, although lacking the amphiphilic topology, behave as anionic surfactants. In pure water, they display "hydrophobic attractions", leading to the formation of aggregates of different sizes and shapes depending on the counterions. When simulated at a water/"oil" interface, the different anions (HCD(-), MeCD(-), CCD(-), and BrCD(-)) are found to be surface active. As a result, the simulated M(n+) counterions (M(n+) = Na(+), K(+), Cs(+), H(3)O(+), UO(2)(2+), Eu(3+)) concentrate on the aqueous side of the interface, forming a "double layer" whose characteristics are modulated by the hydrophobic character of the anion and by M(n+). The highly hydrophilic Eu(3+) or UO(2)(2+) cations that are generally "repelled" by aqueous interfaces are attracted by dicarbollides near the interface, which is crucial as far as the mechanism of assisted cation extraction to the oil phase is concerned. These cations interact with interfacial XCD(-) in their fully hydrated Eu(H(2)O)(9)(3+) and UO(2)(H(2)O)(5)(2+) forms, whereas the less hydrophilic monocharged cations display intimate contacts via their X substituents. The results obtained with the TIP3P and OPLS models for the solvents are confirmed with other water models (TIP5P or a polarizable 4P-Pol water) and with more polar "oil" models. The importance of interfacial phenomena is further demonstrated by simulations with a high oil-water ratio, leading to the formation of a micelle covered with CCD's. We suggest that the interfacial activity of dicarbollides and related hydrophobic anions is an important feature of synergism in liquid-liquid extraction of hard cations (e.g., for nuclear waste partitioning).

  11. 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.

  12. Ordered poly(p-phenylene)/layered double hydroxide ultrathin films with blue luminescence by layer-by-layer assembly.

    PubMed

    Yan, Dongpeng; Lu, Jun; Wei, Min; Han, Jingbin; Ma, Jing; Li, Feng; Evans, David G; Duan, Xue

    2009-01-01

    Lavender layers: A poly(p-phenylene) anionic derivate and exfoliated Mg-Al layered double hydroxide monolayers were assembled into ultrathin films with well-defined blue fluorescence (see picture; the numbers indicate the number of bilayers), long-range order, and high photostability. These films work as multiple quantum-well structures for valence electrons.

  13. 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.

  14. 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.

  15. 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.

  16. [Application of high performance anion exchange chromatography for trace analysis of polarizable anions].

    PubMed

    Mo, Shumin; Liang, Lina; Cai, Yaqi; Mou, Shifen; Wen, Meijuan

    2005-11-01

    Polarizable anions such as Br-, S2O3(2-), I- and SCN- were separated using 45 mmol/L sodium hydroxide solution as the mobile phase on a high hydrophilic IonPac AS16 column. With a pulsed amperometric detector, the detection limits were 0.5, 0.2, 0.05 and 2 microg/L (25.0 microL injected, signal-to-noise ratio of 3) for Br-, S2O3(2-), I- and SCN. The relative standard deviation (RSD) range of trace anions was from 0.8% to 3.7% (n = 9). Under the same chromatographic conditions, these anions were also determined using a suppressed conductivity detector and the detection limits were 1, 1, 2 and 10 microg/L (25 microL injected, signal-to-noise ratio of 3), respectively. The RSD range was from 0.9% to 4.7% (n = 9). Comparing a pulsed amperometric detector with a conductivity detector, the former is 2 to 40 times more sensitive than the latter. For the determination of polarizable anions, a pulsed amperometric detector has higher selectivity, precision and sensitivity.

  17. Morphologies, Preparations and Applications of Layered Double Hydroxide Micro-/Nanostructures

    PubMed Central

    Kuang, Ye; Zhao, Lina; Zhang, Shuai; Zhang, Fazhi; Dong, Mingdong; Xu, Sailong

    2010-01-01

    Layered double hydroxides (LDHs), also well-known as hydrotalcite-like layered clays, have been widely investigated in the fields of catalysts and catalyst support, anion exchanger, electrical and optical functional materials, flame retardants and nanoadditives. This feature article focuses on the progress in micro-/nanostructured LDHs in terms of morphology, and also on the preparations, applications, and perspectives of the LDHs with different morphologies.

  18. 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+}.

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

    DOE PAGES

    Sturgeon, Matthew R.; Macomber, Clay S.; Engtrakul, Chaiwat; ...

    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

  20. 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.

  1. Selective total encapsulation of the sulfate anion by neutral nano-jars.

    PubMed

    Fernando, Isurika R; Surmann, Stuart A; Urech, Alexander A; Poulsen, Alexander M; Mezei, Gellert

    2012-07-11

    Nano-sized toroidal copper(II)-hydroxide/pyrazolate assemblies, lined by H-bond donors on the inside and hydrophobic on the outside, selectively extract sulfate from mixtures with nitrate or perchlorate. Tetrabutylammonium "lids" seal the "nano-jars" and render the encapsulated sulfate anion completely buried and inaccessible, so that it is not precipitated by Ba(2+) ions.

  2. 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...

  3. 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.

  4. 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...

  5. Spherical Monovalent Ions at Aqueous Liquid-Vapor Interfaces: Interfacial Stability and Induced Interface Fluctuations

    PubMed Central

    Ou, Shuching; Hu, Yuan; Patel, Sandeep; Wan, Hongbin

    2014-01-01

    Ion-specific interfacial behaviors of monovalent halides impact processes such as protein denaturation, interfacial stability, surface tension modulation, and as such, their molecular and thermodynamic underpinnings garner much attention. We use molecular dynamics simulations of monovalent anions in water to explore effects on distant interfaces. We observe long-ranged ion-induced perturbations of the aqueous environment as suggested by experiment and theory. Surface stable ions, characterized as such by minima in potentials of mean force computed using umbrella sampling MD simulations, induce larger interfacial fluctuations compared to non-surface active species, conferring more entropy approaching the interface. Smaller anions and cations show no interfacial potential of mean force minima. The difference is traced to hydration shell properties of the anions, and the coupling of these shells with distant solvent. The effects correlate with the positions of the anions in the Hofmeister series (acknowledging variations in force field ability to recapitulate essential underlying physics), suggesting how differences in induced, non-local perturbations of interfaces may be related to different specific-ion effects in dilute biophysical and nanomaterial systems. PMID:24032752

  6. Aniosotropically organized LDH on PVDF: a geometrically templated electrospun substrate for advanced anion conducting membranes.

    PubMed

    Sailaja, G S; Zhang, Peilin; Anilkumar, Gopinathan M; Yamaguchi, Takeo

    2015-04-01

    A bioinspired geometric templating of an electrospun PVDF substrate with hexagonal platelets of Mg-Al layered double hydroxide (LDH), an intrinsic anion conductor, is presented. The distinctive morphology restructures the internal pore geometry and modulates the dynamic wetting profile of PVDF, transforming it into a highly functional substrate for SAFC anion conducting membranes. The membrane fabricated with PVDF-LDH substrate exhibited exceptionally high durability (>140 °C), high anionic conductivity, ion exchange capacity (IEC), restricted swelling, and improved tensile strength, overcoming critical challenges associated with PVDF electrospun substrates and validating its immense potential as a high-temperature-stable and durable substrate for advanced fuel cell membrane applications.

  7. Anions coordinating anions: analysis of the interaction between anionic Keplerate nanocapsules and their anionic ligands.

    PubMed

    Melgar, Dolores; Bandeira, Nuno A G; Bonet Avalos, Josep; Bo, Carles

    2017-02-15

    Keplerates are a family of anionic metal oxide spherical capsules containing up to 132 metal atoms and some hundreds of oxygen atoms. These capsules holding a high negative charge of -12 coordinate both mono-anionic and di-anionic ligands thus increasing their charge up to -42, even up to -72, which is compensated by the corresponding counter-cations in the X-ray structures. We present an analysis of the relative importance of several energy terms of the coordinate bond between the capsule and ligands like carbonate, sulphate, sulphite, phosphinate, selenate, and a variety of carboxylates, of which the overriding component is contributed by solvation/de-solvation effects.

  8. 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.

  9. Chemical stability of hydroxysulphate green rust synthetised in the presence of foreign anions: carbonate, phosphate and silicate

    NASA Astrophysics Data System (ADS)

    Ruby, C.; Gehin, A.; Aissa, R.; Ghanbaja, J.; Abdelmoula, M.; Génin, J.-M. R.

    Hydroxysulphate green rust GR(SO{4/2-}) species were precipitated in the presence of various anions. GR(SO{4/2-}) is stable at ˜pH 7 and is transformed into a mixture of magnetite and ferrous hydroxide when the pH raised at ˜12. In the presence of carbonate species, GR(SO{4/2-}) is partially transformed into a mixture of magnetite and siderite at ˜pH 8.5. This transformation is stopped when silicate anions are present in the solution. As already observed for phosphate anions, the adsorption of silicate anions on the lateral faces of the GR(SO{4/2-}) crystals may explain this stabilization effect. Sulphate anions are easily exchanged by carbonate species at ˜pH 10.5. In contrast, anionic exchange between sulphate and phosphate anions was not observed.

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

    PubMed

    Zhang, Chi; Slater, Lee; Redden, George; Fujita, Yoshiko; Johnson, Timothy; 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.

  11. 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.

  12. 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.

  13. R type anion channel

    PubMed Central

    Diatloff, Eugene; Peyronnet, Rémi; Colcombet, Jean; Thomine, Sébastien; Barbier-Brygoo, Hélène

    2010-01-01

    Plant genomes code for channels involved in the transport of cations, anions and uncharged molecules through membranes. Although the molecular identity of channels for cations and uncharged molecules has progressed rapidly in the recent years, the molecular identity of anion channels has lagged behind. Electrophysiological studies have identified S-type (slow) and R-type (rapid) anion channels. In this brief review, we summarize the proposed functions of the R-type anion channels which, like the S-type, were first characterized by electrophysiology over 20 years ago, but unlike the S-type, have still yet to be cloned. We show that the R-type channel can play multiple roles. PMID:21051946

  14. 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.

  15. 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.

  16. 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.

  17. Layered double hydroxides: an attractive material for electrochemical biosensor design.

    PubMed

    Shan, Dan; Cosnier, Serge; Mousty, Christine

    2003-08-01

    Electrochemical biosensors for phenol determination were developed based on the immobilization of polyphenol oxidase (PPO) within two different clay matrixes, one anionic (layered double hydroxide, LDH) and the other cationic (Laponite). The biosensor based on the enzyme immobilized in [Zn-Al-Cl] LDH shows greater sensitivity (7807 mA M(-1) cm(-2)) and maximum current (492 microA cm(-2)). Biosensor characteristics, such as Michaelis-Menten constant, recycling constant, activation energy, and permeability highlight the advantages of LDH matrixes to immobilize PPO. It appears that LDH provides a favorable environment to PPO activity. The best PPO/[Zn-Al-Cl] configuration was used to determine five different phenol derivatives reaching extremely sensitive detection limits (< or = 1 nM).

  18. Mechanobiology of interfacial growth

    NASA Astrophysics Data System (ADS)

    Ciarletta, P.; Preziosi, L.; Maugin, G. A.

    2013-03-01

    A multiscale analysis integrating biomechanics and mechanobiology is today required for deciphering the crosstalk between biochemistry, geometry and elasticity in living materials. In this paper we derive a unified thermomechanical theory coupling growth processes with mass transport phenomena across boundaries and/or material interfaces. Inside a living system made by two contiguous bodies with varying volumes, an interfacial growth mechanism is considered to force fast but continuous variations of the physical fields inside a narrow volume across the material interface. Such a phenomenon is modelled deriving homogenized surface fields on a growing non-material discontinuity, possibly including a singular edge line. A number of balance laws is derived for imposing the conservation of the thermomechanical properties of the biological system. From thermodynamical arguments we find that the normal displacement of the non-material interface is governed by the jump of a new form of material mechanical-energy flux, also involving the kinetic energies and the mass fluxes. Furthermore, the configurational balance indicates that the surface Eshelby tensor is the tangential stress measure driving the material inhomogeneities on the non-material interface. Accordingly, stress-dependent evolution laws for bulk and interfacial growth processes are derived for both volume and surface fields. The proposed thermomechanical theory is finally applied to three biological system models. The first two examples are focused on stress-free growth problems, concerning the morphogenesis of animal horns and of seashells. The third application finally deals with the stress-driven surface evolution of avascular tumours with heterogeneous structures. The results demonstrate that the proposed theory can successfully model those biological systems where growth and mass transport phenomena interact at different length-scales. Coupling biological, mechanical and geometrical factors, the proposed

  19. 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.

  20. Release behavior and toxicity profiles towards A549 cell lines of ciprofloxacin from its layered zinc hydroxide intercalation compound

    PubMed Central

    2013-01-01

    Background Layered hydroxides salts (LHS), a layered inorganic compound is gaining attention in a wide range of applications, particularly due to its unique anion exchange properties. In this work, layered zinc hydroxide nitrate (LZH), a family member of LHS was intercalated with anionic ciprofloxacin (CFX), a broad spectrum antibiotic via ion exchange in a mixture solution of water:ethanol. Results Powder x-ray diffraction (XRD), Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) confirmed the drug anions were successfully intercalated in the interlayer space of LZH. Specific surface area of the obtained compound was increased compared to that of the host due to the different pore textures between the two materials. CFX anions were slowly released over 80 hours in phosphate-buffered saline (PBS) solution due to strong interactions that occurred between the intercalated anions and the host lattices. The intercalation compound demonstrated enhanced antiproliferative effects towards A549 cancer cells compared to the toxicity of CFX alone. Conclusions Strong host-guest interactions between the LZH lattice and the CFX anion give rise to a new intercalation compound that demonstrates sustained release mode and enhanced toxicity effects towards A549 cell lines. These findings should serve as foundations towards further developments of the brucite-like host material in drug delivery systems. PMID:23849189

  1. 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

  2. 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.

  3. Aerosol-assisted self-assembly of hybrid Layered Double Hydroxide particles into spherical architectures.

    PubMed

    Prevot, Vanessa; Szczepaniak, Claire; Jaber, Maguy

    2011-04-15

    Acetate intercalated NiAl-Layered Double Hydroxide nanoparticles were prepared by polyol process and further used as building blocks to form hybrid LDH spheres by a spray drying technique. The spherical aggregated LDH particles display a polydispersed size with a diameter ranging from 47 nm to 2 μm. The analysis of the thermal behavior evidenced that the spherical form was maintained upon calcination up to 1100°C, giving rise to derived mixed oxide (NiO+NiAl(2)O(4)) nanospheres. Interestingly, the spherical morphology of the LDH materials was also retained during anion exchange process. The replacement of the intercalated acetate anion by of a voluminous anion such as dodecylsulfate induces an increase of the nanosphere mean diameter of 65%. The different materials were deeply characterized using X-ray diffraction, FTIR spectroscopy, scanning and transmission electron microscopies, dynamic light scattering, thermal analysis and nitrogen sorption.

  4. 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. Copyright © 2014 Elsevier Inc. All rights reserved.

  5. Anion-π catalysis.

    PubMed

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

    2014-02-05

    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

  6. Interfacial Instabilities in Evaporating Drops

    NASA Astrophysics Data System (ADS)

    Moffat, Ross; Sefiane, Khellil; Matar, Omar

    2007-11-01

    We study the effect of substrate thermal properties on the evaporation of sessile drops of various liquids. An infra-red imaging technique was used to record the interfacial temperature. This technique illustrates the non-uniformity in interfacial temperature distribution that characterises the evaporation process. Our results also demonstrate that the evaporation of methanol droplets is accompanied by the formation of wave-trains in the interfacial temperature field; similar patterns, however, were not observed in the case of water droplets. More complex patterns are observed for FC-72 refrigerant drops. The effect of substrate thermal conductivity on the structure of the complex pattern formation is also elucidated.

  7. 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.

  8. 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

  9. Dynamics of interfacial pattern formation

    NASA Technical Reports Server (NTRS)

    Ben-Jacob, E.; Goldenfeld, N.; Langer, J. S.; Schon, G.

    1983-01-01

    A phenomenological model of dendritic solidification incorporating interfacial kinetics, crystalline anisotropy, and a local approximation for the dynamics of the thermal diffusion field is proposed. The preliminary results are in qualitative agreement with natural dendrite-like pattern formation.

  10. 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.

  11. Role of interface structure and interfacial defects in oxide scale growth

    SciTech Connect

    Pieraggi, B.; Rapp, R.A.; Hirth, J.P.

    1995-08-01

    Recent studies of the structure and dynamics of solid-solid interfaces have provided some understanding about the role of the scale-metal interface in the growth of reaction product scales on pure metals. The action of interfacial defects (misfit dislocations, misorientation dislocations and disconnections) in the creation and annihilation of the point defects supporting the diffusional growth of scales is considered. Anion point defects (vacancies/interstitials) supporting scale growth by anion diffusion are annihilated/created by the climb of misorientation dislocations or disconnections in the scale at the interface. For scale growth by cation diffusion, cation point defects (vacancies/interstitials) can be annihilated/created by the climb of interfacial misfit or misorientation dislocations in the metal. Because of their necessarily high density, in most cases, the dominant climb of misfit dislocations would be favored. The blocking of interfacial reaction steps can be a means to retard the scaling kinetics and to alter the fundamental scaling mode. For instance, the interfacial segregation of large reactive element ions can point the interface dislocations, an action which poisons the usual interfacial reaction step. Such considerations are consistent with the well-known phenomena ascribed to the reactive element effect (REE).

  12. 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.

  13. 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.

  14. 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.

  15. Complex anion inclusion compounds: flexible anion-exchange materials.

    PubMed

    Williams, Edward R; Leithall, Rebecca M; Raja, Robert; Weller, Mark T

    2013-01-11

    Copper chloropyrophosphate frameworks have been synthesised with a wide variety of complex inorganic anions trapped in a large, flexible, one-dimensional pore, with anions including chloride, bromide, phosphate and the complex metal halo-anions PtCl(4)(2-), PdBr(4)(2-), CuCl(4)(2-) and AuCl(4)(-).

  16. Thermodynamics of Volatile Silicon Hydroxides Studied

    NASA Technical Reports Server (NTRS)

    Copland, Evan H.; Opila, Elizabeth J.; Jacobson, Nathan S.

    2001-01-01

    Silicon-based ceramics are promising candidate structural materials for heat engines. The long-term stability of these materials to environmental degradation is dependent on the formation and retention of a protective SiO2 layer. It is well known that SiO2 forms stable volatile hydroxides in the presence of water vapor at elevated temperatures. Combustion conditions, which characteristically are at high velocities, contain significant water vapor pressures, and high temperatures tend to promote continuous formation of these hydroxides with resulting material degradation. For the degradation of silicon-based ceramics to be predicted, accurate thermodynamic data on the formation of silicon hydroxides are needed.

  17. Properties of oxide-hydroxide sintered ceramics

    NASA Astrophysics Data System (ADS)

    Levkov, R. V.; Kulkov, S. N.

    2017-02-01

    In this paper the study of porous ceramics obtained from aluminum hydroxide with gibbsite modification is presented. 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. It was shown that compressive strength of alumina ceramics increases by 40 times with decreasing the pore volume from 65 to 15%. 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.

  18. Smart interfacial bonding alloys

    SciTech Connect

    R. Q. Hwang; J. C. Hamilton; J. E. Houston

    1999-04-01

    The goal of this LDRD was to explore the use of the newly discovered strain-stabilized 2-D interfacial alloys as smart interface bonding alloys (SIBA). These materials will be used as templates for the heteroepitaxial growth of metallic thin films. SIBA are formed by two metallic components which mix at an interface to relieve strain and prevent dislocations from forming in subsequent thin film growth. The composition of the SIBA is determined locally by the amount of strain, and therefore can react smartly to areas of the highest strain to relieve dislocations. In this way, SIBA can be used to tailor the dislocation structure of thin films. This project included growth, characterization and modeling of films grown using SIBA templates. Characterization will include atomic imaging of the dislocations structure, measurement of the mechanical properties of the film using interface force microscopy (IFM) and the nanoindenter, and measurement of the electronic structure of the SIBA with synchrotron photoemission. Resistance of films to sulfidation and oxidation will also be examined. The Paragon parallel processing computer will be used to calculate the structure of the SIBA and thin films in order to develop ability to predict and tailor SIBA and thin film behavior. This work will lead to the possible development of a new class of thin film materials with properties tailored by varying the composition of the SIBA, serving as a buffer layer to relieve the strain between the substrate and the thin film. Such films will have improved mechanical and corrosion resistance allowing application as protective barriers for weapons applications. They will also exhibit enhanced electrical conductivity and reduced electromigration making them particularly suitable for application as interconnects and other electronic needs.

  19. 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.

  20. Iron-Substituted Nickel Oxyhydroxides and Hydroxides Obtained by Chimie Douce

    NASA Astrophysics Data System (ADS)

    Demourgues-Guerlou, L.; Braconnier, J. J.; Delmas, C.

    1993-06-01

    New iron-substituted nickel hydroxides have been prepared by chimie douce reactions from the NaNi 1- xFe xO 2 precursor phases. Oxidizing hydrolysis of these materials leads to γ-oxyhydroxides which are then easily reduced to hydroxides. A crystal chemical study of the three material classes has been performed. The precursor phases crystallize in the rhombohedral system for x ≥ 0.2, while the lower iron concentrations lead to a monoclinic distortion due to the Jahn-Teller effect of Ni III ions. This distortion is not observed in the case of the γ phases. For x ≥ 0.2, the hydroxides also crystallize in the rhombohedral system, whereas for smaller iron concentrations, interstratified-type structures similar to those commonly found among the layered double hydroxide minerals family are obtained. Chemical analysis and magnetic property study have shown the presence of (1 - x )Ni 2+ and xFe 3+ ions within the slab. Anions (mainly CO 2-3 ions) are inserted into the intersheet space in order to compensate the excess positive charge due to Fe 3+ ions.

  1. Determination of NAPL-water interfacial areas in well-characterized porous media.

    PubMed

    Dobson, Richard; Schroth, Martin H; Oostrom, Mart; Zeyer, Josef

    2006-02-01

    The nonaqueous-phase liquid (NAPL)-water interfacial area is an important parameter which influences the rate of NAPL dissolution in porous media. The aim of this study was to generate a set of baseline data for specific interfacial area for a two-phase-entrapped NAPL-water system in well-characterized porous media and subsequently use these data to evaluate two current theoretical models. The first model tested distributes entrapped NAPL over the pore classes based on Land's algorithm and assumes the resulting blobs to be spherical. The other model is thermodynamically based, assuming that reversible work done on the system results in an increase in interfacial area, such that the area between drainage and imbibition retention curves can be related to the interfacial area. Interfacial tracer tests (IFTT) were used to measure specific entrapped NAPL (hexadecane)-water interfacial areas in columns packed with four grades (12/20, 20/30, 30/40, 40/50) of silica sand. By use of the anionic surfactant dihexylsulfosuccinate (Aerosol MA80), IFTT gave specific interfacial areas between 58 cm(-1) for the finest sand and 16 cm(-1) for the coarsest, compared to values of between 33 and 7 cm(-1) for the first model and between 19 and 5 cm(-1) for the thermodynamic model. Results from the literature suggest that nonspherical blobs shapes occur relatively frequently; hence it is reasonable to suggest that the assumption of spherical NAPL blobs may explain the underprediction by the first model. The thermodynamic model underestimates the interfacial area because it assumes that entrapment occurs only within the largest pores. A modified version of the latter model, allowing entrapment across all pore classes, yielded values between 58 and 13 cm(-1). Of the models tested the modified thermodynamic model best predicts the interfacial area.

  2. Determination of NAPL-Water Interfacial Areas in Well-Characterized Porous Media

    SciTech Connect

    Dobson, Richard; Schroth, Martin H.; Oostrom, Mart; Zeyer, Josef

    2006-02-01

    The nonaqueous-phase liquid (NAPL)-water interfacial area is an important parameter which influences the rate of NAPL dissolution in porous media. The aim of this study was to generate a set of baseline data for specific interfacial area for a two-phase entrapped NAPL-water system in well-characterized porous media, and subsequently use these data to evaluate two current theoretical models. The first model tested distributes entrapped NAPL over the pore classes based on Land's algorithm and assumes the resulting blobs to be spherical. The other model is thermodynamically based, assuming that reversible work done on the system results in an increase in interfacial area, such that the area between drainage and imbibition retention curves can be related to the interfacial area. Interfacial tracer tests (IFTT) were used to measure specific entrapped NAPL (hexadecane)-water interfacial areas in columns packed with four grades (12/20, 20/30, 30/40, 40/50) of silica sand. Using the anionic surfactant dihexylsulfosuccinate (Aerosol? MA80), IFTT gave specific interfacial areas between 58 cm-1 for the finest sand and 16 cm-1 for the coarsest, compared to values of between 33 cm-1 and 7 cm-1 for the first model and between 19 cm-1 and 5 cm-1 for the thermodynamic model. Results from the literature suggest that non-spherical blobs shapes occur relatively frequently; hence it is reasonable to suggest that the assumption of spherical NAPL blobs may explain the underprediction by the first model. The thermodynamic model underestimates the interfacial area because it assumes that entrapment occurs only within the largest pores. A modified version of the latter model, allowing entrapment across all pore classes, yielded values between 58 cm-1 and 13 cm-1. Of the models tested the modified thermodynamic model best predicts the interfacial area.

  3. 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.

  4. Tungstocobaltate-pillared layered double hydroxides: Preparation, characterization, magnetic and catalytic properties

    SciTech Connect

    Wei Xiaocui; Fu Youzhi; Xu Lin Li Fengyan; Bi Bo; Liu Xizheng

    2008-06-15

    A new polyoxometalate anion-pillared layered double hydroxide (LDH) was prepared by aqueous ion exchange of a Mg-Al LDH precursor in nitrate form with the tungstocobaltate anions [CoW{sub 12}O{sub 40}]{sup 5-}. The physicochemical properties of the product were characterized by the methods of powder X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis and cyclic voltammetry. It was confirmed that [CoW{sub 12}O{sub 40}]{sup 5-} was intercalated between the brucite-type layers of the LDHs without a change in the structure. Magnetic measurement shows the occurrence of antiferromagnetic interactions between the magnetic centers. The investigation of catalytic performance for this sample exhibits high activity for the oxidation of benzaldehyde by hydrogen peroxide. - Graphical abstract: A tungstocobaltate anion [CoW{sub 12}O{sub 40}]{sup 5-} pillared layered double hydroxide (LDH) was prepared by aqueous ion exchange with a Mg-Al LDH precursor in nitrate form, demonstrating that [CoW{sub 12}O{sub 40}]{sup 5-} was intercalated between the brucite-type layers of the LDHs without change in structure. Magnetic measurement shows the occurrence of antiferromagnetic interactions between the magnetic centers. The investigation of catalytic performance for this sample exhibits high activity for the oxidation of benzaldehyde by hydrogen peroxide.

  5. Chimie Douce Reactions: A New Route to Obtain Well Crystallized Layer Double Hydroxides

    NASA Astrophysics Data System (ADS)

    Delmas, C.; Borthomieu, Y.

    1993-06-01

    Layer double hydroxides (LDHs) have been obtained by chimie douce reactions from the NaNi 1- yCo yO 2 cobalt substituted sodium nickelate (0 ≤ y ≤ 0.5). These materials exhibit the general formula Ni 1-y Co y(OH) 2Xy/n, zH 2O, X n- = CO 2-3, NO -3, Cl -, OH -, SO 2-4 …. The X n- anions and the water molecules are inserted between the hydroxide slabs. The Ni 1- yCo yO 2 slabs are built up during the high temperature preparation of the sodium nickelate, while the anions are inserted later on during the chimie douce reaction. It follows that a wider range of materials can be obtained than in the case of classical precipitation reactions. Moreover, the materials are well crystallized. The LDHs have been characterized by X-ray diffraction and by IR spectroscopy. The observed anion selectivity is discussed on the basis of electrostatic interactions and steric effects.

  6. 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

  7. Photodetachment of Lanthanide Oxide Anions

    NASA Astrophysics Data System (ADS)

    Covington, A. M.; Emmons, E. D.; Kraus, R. G.; Thompson, J. S.; Calabrese, D.; Davis, V. T.

    2007-06-01

    Laser photodetached electron spectroscopy (LPES) has been used to study the structure and collision properties of lanthanide oxide anions including LaOn^- and CeOn^-. Preliminary photoelectron spectra from these anions will be presented along with ion beam production data from these and other lanthanide oxide anions.

  8. 21 CFR 184.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... a white precipitate by the addition of sodium hydroxide to a water soluble magnesium salt or by hydration of reactive grades of magnesium oxide. (b) The ingredient meets the specifications of the Food...

  9. 21 CFR 184.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... is prepared as a white precipitate by the addition of sodium hydroxide to a water soluble magnesium salt or by hydration of reactive grades of magnesium oxide. (b) The ingredient meets the specifications...

  10. Calcium hydroxide liners: a literature review

    PubMed Central

    Arandi, Naji Ziad

    2017-01-01

    Objective This review integrates the literature on cavity liners and current concepts of pulp protection with the aim of establishing a better understanding of the role of calcium hydroxide as a cavity liner. Materials and methods A search was conducted through PubMed, MEDLINE, and Ovid for articles with the criteria for the following terms: cavity liners and bases, pulp protection, and calcium hydroxide liners. No specific inclusion or exclusion criteria were applied as to what articles would be included in this review. It was hoped that the extent of the literature reviewed would be as comprehensive as possible. Conclusion This review underlines the fact that calcium hydroxide liners should only be used in the deepest spots in the cavity where the remaining dentine thickness is ≤0.5 mm. A protective layer of resin-modified glass ionomer should always follow the application of calcium hydroxide liners. PMID:28761378

  11. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Aluminum hydroxide nanoparticles show a stronger vaccine adjuvant activity than traditional aluminum hydroxide microparticles

    PubMed Central

    Li, Xinran; Aldayel, Abdulaziz M.; Cui, Zhengrong

    2013-01-01

    Aluminum hydroxide is used as a vaccine adjuvant in various human vaccines. Unfortunately, despite its favorable safety profile, aluminum hydroxide can only weakly or moderately potentiate antigen-specific antibody responses. When dispersed in an aqueous solution, aluminum hydroxide forms particulates of 1–20 µm. There is increasing evidence that nanoparticles around or less than 200 nm as vaccine or antigen carriers have a more potent adjuvant activity than large microparticles. In the present study, we synthesized aluminum hydroxide nanoparticles of 112 nm. Using ovalbumin and Bacillus anthracis protective antigen protein as model antigens, we showed that protein antigens adsorbed on the aluminum hydroxide nanoparticles induced a stronger antigen-specific antibody response than the same protein antigens adsorbed on the traditional aluminum hydroxide microparticles of around 9.3 µm. The potent adjuvant activity of the aluminum hydroxide nanoparticles was likely related to their ability to more effectively facilitate the uptake of the antigens adsorbed on them by antigen-presenting cells. Finally, the local inflammation induced by aluminum hydroxide nanoparticles in the injection sites was milder than that induced by microparticles. Simply reducing the particle size of the traditional aluminum hydroxide adjuvant into nanometers represents a novel and effective approach to improve its adjuvanticity. PMID:24188959

  13. Aluminum hydroxide nanoparticles show a stronger vaccine adjuvant activity than traditional aluminum hydroxide microparticles.

    PubMed

    Li, Xinran; Aldayel, Abdulaziz M; Cui, Zhengrong

    2014-01-10

    Aluminum hydroxide is used as a vaccine adjuvant in various human vaccines. Unfortunately, despite its favorable safety profile, aluminum hydroxide can only weakly or moderately potentiate antigen-specific antibody responses. When dispersed in an aqueous solution, aluminum hydroxide forms particulates of 1-20μm. There is increasing evidence that nanoparticles around or less than 200nm as vaccine or antigen carriers have a more potent adjuvant activity than large microparticles. In the present study, we synthesized aluminum hydroxide nanoparticles of 112nm. Using ovalbumin and Bacillus anthracis protective antigen protein as model antigens, we showed that protein antigens adsorbed on the aluminum hydroxide nanoparticles induced a stronger antigen-specific antibody response than the same protein antigens adsorbed on the traditional aluminum hydroxide microparticles of around 9.3μm. The potent adjuvant activity of the aluminum hydroxide nanoparticles was likely related to their ability to more effectively facilitate the uptake of the antigens adsorbed on them by antigen-presenting cells. Finally, the local inflammation induced by aluminum hydroxide nanoparticles in the injection sites was milder than that induced by microparticles. Simply reducing the particle size of the traditional aluminum hydroxide adjuvant into nanometers represents a novel and effective approach to improve its adjuvanticity. © 2013.

  14. Synthesis and UV absorption properties of 5-sulfosalicylate-intercalated Zn-Al layered double hydroxides

    SciTech Connect

    Zhang Linyan; Lin Yanjun; Tuo Zhenjun; Evans, David G.; Li Dianqing

    2007-04-15

    5-sulfosalicylic acid (SSA) anions have been intercalated into layered double hydroxides (LDHs) by an anion-exchange reaction using ZnAl-NO{sub 3}-LDHs as a precursor. The samples were characterized by XRD, FT-IR, TG-DTA/MS and UV-visible spectroscopy. The results show that the NO{sub 3} {sup -} anions in the precursor have been completely replaced by SSA anions to give ZnAl-SSA-LDHs having a high degree of crystallinity. Detailed studies reveal the existence of a supramolecular structure in ZnAl-SSA-LDHs involving electrostatic attraction between opposite charges, hydrogen bonding and other weak chemical bonding interactions between host layers and SSA anions. The thermal stability of ZnAl-SSA-LDHs is considerably enhanced compared with that of a mixture of ZnAl-NO{sub 3}-LDHs and SSA. After addition of 2.0 wt% ZnAl-SSA-LDHs to polypropylene (PP), the resistance of the polymer to UV degradation is significantly improved. - Graphical abstract: UV-visible absorbance curves of SSA (a), ZnAl-NO{sub 3}-LDHs precursor (b) and ZnAl-SSA-LDHs (c)

  15. 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.

  16. 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.

  17. 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.

  18. Simultaneous determination of NH4+, NO2(-) and NO3(-) by ion-exclusion/anion-exchange chromatography on a strongly basic anion-exchange resin with basic eluent.

    PubMed

    Mori, Masanobu; Hironaga, Takahiro; Itabashi, Hideyuki; Nakatani, Nobutake; Kozaki, Daisuke; Tanaka, Kazuhiko

    2012-04-01

    Ion-exclusion/anion-exchange chromatography (IEC/AEC) on a combination of a strongly basic anion-exchange resin in the OH(-)-form with basic eluent has been developed. The separation mechanism is based on the ion-exclusion/penetration effect for cations and the anion-exchange effect for anions to anion-exchange resin phase. This system is useful for simultaneous separation and determination of ammonium ion (NH4+), nitrite ion (NO2(-)), and nitrate ion (NO3(-)) in water samples. The resolution of analyte ions can be manipulated by changing the concentration of base in eluent on a polystyrene-divinylbenzene based strongly basic anion-exchange resin column. In this study, several separation columns, which consisted of different particle sizes, different functional groups and different anion-exchange capacities, were compared. As the results, the separation column with the smaller anion-exchange capacity (TSKgel Super IC-Anion) showed well-resolved separation of cations and anions. In the optimization of the basic eluent, lithium hydroxide (LiOH) was used as the eluent and the optimal concentration was concluded to be 2 mmol/L, considering the resolution of analyte ions and the whole retention times. In the optimal conditions, the relative standard deviations of the peak areas and the retention times of NH4+, NO2(-), and NO3(-) ranged 1.28% - 3.57% and 0.54% - 1.55%, respectively. The limits of detection at signal-to-noise of 3 were 4.10 micromol/L for NH4+, 1.87 micromol/L for NO2(-) and 2.83 micromol/L for NO3(-).

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. X-ray diffraction investigations of deformations and dislocation configuration in calcium hydroxide crystallites of concrete

    NASA Astrophysics Data System (ADS)

    Harutyunyan, V. S.; Abovyan, E. S.; Monteiro, P. J. M.

    2003-12-01

    On the bases of proposed theoretical approach for analysis of X-ray diffraction spectra the peculiarities of morphology, deformations, stresses and dislocation configuration of calcium hydroxide crystallites of interfacial transition zone in high-strength concrete (the water-cement ratio is about 0.35) are investigated. It is determined that the (0001) dislocation slip planes dividing the calcium hydroxide crystallites into coherent domains are arranged in them quasi-periodically along c-crystallographic axis. For dislocation configuration in crystallites the so-called multilayer dislocation multipole configuration is proposed. From the reconstructed strain distribution function of coherent domains it was concluded that the most part of them are subjected to compressive strain caused most probably due to drying shrinkage phenomenon. The intrinsic stresses of crystallites are estimated for uniaxial compressive, hydrostatic compressive, and shear types of deformation. A possibility for dislocation pile-ups formation in (0001) atomic planes (domain boundaries) is considered theoretically as well. From comparative analyses of intrinsic stresses of crystallites with their ultimate stresses it is assumed that the main mechanism leading to failure of calcium hydroxide both in interfacial transition zone and cement paste of concrete are dislocation pile-ups which form against phase inclusions because of action of external shear stresses. The results are obtained and compared for two samples with granite and smoky quartz aggregates. It is assumed that the proposed theoretical approach for analysis of X-ray diffraction spectra could be perspective especially for investigations of nanostructured polycrystalline materials with a columnar structure. (

  4. Synthesis of nanocomposite 2-methyl-4-chlorophenoxyacetic acid with layered double hydroxide: physicochemical characterization and controlled release properties

    NASA Astrophysics Data System (ADS)

    Sarijo, Siti Halimah; Ghazali, Sheikh Ahmad Izaddin Sheikh Mohd; Hussein, Mohd Zobir; Sidek, Norizzah Jaafar

    2013-01-01

    A new organic-inorganic hybrid nanocomposite Zn-Al-MCPA-layered double hydroxide (ZAM) was prepared by intercalation of 2-methyl-4-chlorophenoxyacetic acid (MCPA) into Zn-Al-layered double hydroxide (ZAL) at various concentration of MCPA ranging from 0.1 to 0.7 M. The pH of the synthesis was kept constant at 7.5. Well-ordered hybrid nanocomposite was obtained with 0.4 M MCPA with an expansion of basal spacing from 8.9 Å in the ZAL to 19.7 Å in the resulting nanocomposite. The FTIR spectra of the nanocomposite show resemblance peaks of the MCPA and Zn-Al-layered double hydroxide indicating the inclusion of MCPA into the layered double hydroxide. The average particle size of ZAL and ZAM in this study was 115 and 128 nm, respectively. Percentage loading of MCPA was found to be 45.0 % (w/w), calculated based on the percentage of carbon in the sample. The release of MCPA into various aqueous solution was found to be dependent to the anion in the aqueous solution in the order of phosphate > sulfate > chloride with the percentage release of 80, 44, and 8 %, respectively. This study shows that Zn-Al-layered double hydroxide can be used as a host carrier for herbicide, MCPA, with controlled release capability.

  5. 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.

  6. 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.

  7. Dentin-cement Interfacial Interaction

    PubMed Central

    Atmeh, A.R.; Chong, E.Z.; Richard, G.; Festy, F.; Watson, T.F.

    2012-01-01

    The interfacial properties of a new calcium-silicate-based coronal restorative material (Biodentine™) and a glass-ionomer cement (GIC) with dentin have been studied by confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), micro-Raman spectroscopy, and two-photon auto-fluorescence and second-harmonic-generation (SHG) imaging. Results indicate the formation of tag-like structures alongside an interfacial layer called the “mineral infiltration zone”, where the alkaline caustic effect of the calcium silicate cement’s hydration products degrades the collagenous component of the interfacial dentin. This degradation leads to the formation of a porous structure which facilitates the permeation of high concentrations of Ca2+, OH-, and CO32- ions, leading to increased mineralization in this region. Comparison of the dentin-restorative interfaces shows that there is a dentin-mineral infiltration with the Biodentine, whereas polyacrylic and tartaric acids and their salts characterize the penetration of the GIC. A new type of interfacial interaction, “the mineral infiltration zone”, is suggested for these calcium-silicate-based cements. PMID:22436906

  8. 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.

  9. Theoretical simulation of reduction mechanism of graphene oxide in sodium hydroxide solution.

    PubMed

    Chen, Chu; Kong, Weixin; Duan, Hai-Ming; Zhang, Jun

    2014-07-07

    Based on a density functional theory simulation, we proposed a reduction mechanism of graphene oxide (GO) under a sodium hydroxide solution containing anions (OH(-)), cations (Na(+)) and neutral H2O molecules as main components. OH(-) anion can interact with hydroxyl in GO and transfer electrons to the graphene sheet, resulting in negatively charged GO, and these electrons obviously lower the barrier of the ring-opening reaction of epoxy. Na(+) cations can be attracted by the negatively charged GO, and this reaction is equivalent to the one between metallic Na and GO. The opened epoxy is reduced with the assistance of Na(+) cation and water molecule. In such a reduction process, NaOH can be viewed as a catalyst and more defects should be formed because of these diffused epoxies on the negatively charged graphene sheet. Our results may be helpful to understand further the nature of the reduction of GO among various reducing agents.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

    Wang, Qian; Feng, Yongjun; Feng, Junting; Li, Dianqing

    2011-06-01

    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.

  12. Atomistic simulation of nanoporous layered double hydroxide materials and their properties. I. Structural modeling.

    PubMed

    Kim, Nayong; Kim, Yongman; Tsotsis, Theodore T; Sahimi, Muhammad

    2005-06-01

    An atomistic model of layered double hydroxides, an important class of nanoporous materials, is presented. These materials have wide applications, ranging from adsorbents for gases and liquid ions to nanoporous membranes and catalysts. They consist of two types of metallic cations that are accommodated by a close-packed configuration of OH- and other anions in a positively charged brucitelike layer. Water and various anions are distributed in the interlayer space for charge compensation. A modified form of the consistent-valence force field, together with energy minimization and molecular dynamics simulations, is utilized for developing an atomistic model of the materials. To test the accuracy of the model, we compare the vibrational frequencies, x-ray diffraction patterns, and the basal spacing of the material, computed using the atomistic model, with our experimental data over a wide range of temperature. Good agreement is found between the computed and measured quantities.

  13. Atomistic simulation of nanoporous layered double hydroxide materials and their properties. I. Structural modeling

    NASA Astrophysics Data System (ADS)

    Kim, Nayong; Kim, Yongman; Tsotsis, Theodore T.; Sahimi, Muhammad

    2005-06-01

    An atomistic model of layered double hydroxides, an important class of nanoporous materials, is presented. These materials have wide applications, ranging from adsorbents for gases and liquid ions to nanoporous membranes and catalysts. They consist of two types of metallic cations that are accommodated by a close-packed configuration of OH- and other anions in a positively charged brucitelike layer. Water and various anions are distributed in the interlayer space for charge compensation. A modified form of the consistent-valence force field, together with energy minimization and molecular dynamics simulations, is utilized for developing an atomistic model of the materials. To test the accuracy of the model, we compare the vibrational frequencies, x-ray diffraction patterns, and the basal spacing of the material, computed using the atomistic model, with our experimental data over a wide range of temperature. Good agreement is found between the computed and measured quantities.

  14. Mixed Anion Heterostructure Materials

    DTIC Science & Technology

    2004-10-01

    data presented Sb(g) Sb(ads) Sb(s) Kads D (1) (2)Very low + GaAs no reaction ( 3 ) kexch 33 for As2 which indicates that the...Kads D (1) (2) ( 3 ) Anion Exchange kexch (4) Isoelectronic AsSb formation Favoured by As4 +As GaAsySb1-y + Sby(s) GaSb1-y + AsSby(s) +As kiso (5...experiment implemented for this investigation provided a basis for modeling the P(g) P(ads) P(s) + GaAs Kads D (1) (2) ( 3 ) kexch (4) +P GaPyAs1-y

  15. 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.

  16. Hydroxide and Proton Migration in Aquaporins

    PubMed Central

    Jensen, Morten Ø.; Röthlisberger, Ursula; Rovira, Carme

    2005-01-01

    Hypothetical hydroxide and proton migration along the linear water chain in Aquaporin GlpF from Escherichia coli are studied by ab initio Car-Parrinello molecular dynamics simulations. It is found that the protein stabilizes a bipolar single file of water. The single file features a contiguous set of water-water hydrogen bonds in which polarization of the water molecules vary with position along the channel axis. Deprotonation of the water chain promotes the reorientation of water molecules while the hydroxide ion rapidly migrates by sequentially accepting protons from the neighboring water molecules. The hydroxide ion is not attracted by a conserved, channel-lining arginine residue, but is immobilized at two centrally located, conserved Asparagine-Proline-Alanine motifs where fourfold coordination stabilizes the ion. Hydroxide transition from the channel vestibules into the channel lumen is strongly influenced by electrostatic coupling to two conserved oppositely aligned macrodipoles. This suggests that the macrodipole's negative poles play a role in preventing hydroxide ions from entering into the channel's inner vestibules. Water protonation within the lumen facilitates water reorientation and subsequent proton expelling occurs. In the periplasmic half-channel, expelling occurs via the Grotthuss mechanism. Protonation within the cytoplasmic half-channel implies wire-breakage at the Asn-Pro-Ala motifs. The proton is here diffusively rejected as (H5O2)+. PMID:15951380

  17. 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.

  18. 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.

  19. 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.

  20. Characterisation of gunshot residue from three ammunition types using suppressed anion exchange chromatography.

    PubMed

    Gilchrist, Elizabeth; Jongekrijg, Fleur; Harvey, Laura; Smith, Norman; Barron, Leon

    2012-09-10

    Gunshot residue (GSR) is commonly analysed in forensic casework using either scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) or gas chromatography-mass spectrometry (GC-MS). Relatively little work has been reported on the post-discharge GSR content of non-metallic inorganic or low molecular weight organic anions to distinguish between different ammunition types. The development of an analytical method using suppressed micro-bore anion exchange chromatography (IC) is presented for the analysis of GSR. A hydroxide gradient was optimised for the separation of 19 forensically relevant organic and inorganic anions in <23min and sensitivities of the order of 0.12-3.52ng of anion detected for all species were achieved. Along with an optimised extraction procedure, this method was applied to the analysis of post-ignition residues from three selected ammunition types. By profiling and comparing the anionic content in each ammunition residue, the possibility to distinguish between each type using their anionic profiles and absolute weight is presented. The potential for interference is also discussed with respect to sample types which are typically problematic in the analysis of GSR using SEM-EDX and GC-MS. To the best of our knowledge this represents the first study on the analysis of inorganic anions in GSR using suppressed ion chromatography.

  1. Anion exchangers with negatively charged functionalities in hyperbranched ion-exchange layers for ion chromatography.

    PubMed

    Uzhel, Anna S; Zatirakha, Alexandra V; Smirnov, Konstantin N; Smolenkov, Alexandr D; Shpigun, Oleg A

    2017-01-27

    Novel pellicular poly(styrene-divinylbenzene)-based (PS-DVB) anion exchangers with covalently-bonded hyperbranched functional ion-exchange layers containing negatively charged functionalities are obtained and examined. The hyperbranched coating is created on the surface of aminated PS-DVB substrate by repeating the modification cycles including alkylation with 1,4-butanediol diglycidyl ether (1,4-BDDGE), and amination of the terminal epoxide rings with methylamine (MA) or glycine (Gly). The influence of the position and the number of the layers with glycine, as well as of the total number of the layers of amine in the coating on the chromatographic properties of the obtained stationary phases is investigated. Chromatographic performance of the obtained stationary phases is evaluated using the model mixtures of inorganic and organic anions with hydroxide eluent. It is shown that the best selectivity toward weakly retained organic acids and oxyhalides is possessed by the anion exchanger obtained after 5 modification cycles, with glycine being used in the first one. Such anion exchanger packed in 25-cm long column is capable of separating 22 anions in 58min including 7 standard anions, mono-, di- and trivalent organic acids, oxyhalides, and some other double- and triple-charged anions.

  2. 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 -}.

  3. 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.

  4. 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.

  5. 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.

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

    SciTech Connect

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

    2016-01-15

    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. - Graphical abstract: Amino acid anion-Ca(II)Fe(III)-LDHs were successfully prepared by a two-step milling procedure. - Highlights: • Synthesis of pristine and amino acid intercalated CaFe-LDHs by two-step milling. • Identifying the optimum synthesis and intercalation parameters. • Characterisation of the samples with a range of instrumental methods.

  7. 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.

  8. Intercalation of IR absorber into layered double hydroxides: Preparation, thermal stability and selective IR absorption

    SciTech Connect

    Zhu, Haifeng; Tang, Pinggui; Feng, Yongjun; Wang, Lijing; Li, Dianqing

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer PMIDA anions were intercalated into Mg{sub 2}Al-NO{sub 3} LDH by anion-exchange method. Black-Right-Pointing-Pointer The prepared material has highly selective IR absorption property in 9-11 {mu}m. Black-Right-Pointing-Pointer The obtained material has practical applications as heat-retaining additive. -- Abstract: N-phosphonomethyl aminodiacetic acid (PMIDA) was intercalated into the interlayer spacing of layered double hydroxides (LDH) by an anion-exchange method. The intercalated LDHs were characterized by various techniques such as powder X-ray diffraction (XRD), FT-IR spectroscopy, elemental analysis and simultaneous thermogravimetric and mass spectrometry (TG-MS) in details. The results show the formation of Mg{sub 2}Al-PMIDA LDH based on the expansion of d-spacing from 0.89 nm to 1.22 nm and the disappearance of the characteristic IR absorption band at 1384 cm{sup -1} for NO{sub 3}{sup -} anions. The incorporation of Mg{sub 2}Al-PMIDA LDH into the low density polyethylene (LDPE) as an additive enhances the selectivity of IR absorption in the main wavelength region 9-11 {mu}m for radiant heat loss at night. Mg{sub 2}Al-PMIDA LDH as a heat-retaining additive has practical application in agricultural plastic films.

  9. Computer simulation of interlayer arrangement in cinnamate intercalated layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Greenwell, H. C.; Jones, W.; Newman, S. P.; Coveney, P. V.

    2003-02-01

    The interlayer arrangements of Mg-Al layered double hydroxides (LDHs) containing trans-cinnamate anions have been studied using molecular dynamics computer simulations. A modified version of the Dreiding forcefield was used to perform simulations of models with Mg/Al ratios of 2,3 and 6. For each Mg/Al ratio, two hydration states of 20 and 30 wt% water content were modelled. Close contacts between the olefinic carbons of the anion were analysed in an attempt to rationalize the potential outcome of the [2+2] photo-induced dimerization of the anions. In all instances, except for the model with Mg/Al=6 and 20 wt% water, the arrangement of the dimer pairs showed that syn-head-to-tail dimer formation was unfavourable. Preferred orientation of dimer pairs towards formation of head-to-head dimers was observed to undergo a transition from strongly favouring the syn-head-to-head dimer at low Mg/Al ratios to greater selectivity for the anti-head-to-head dimer with increasing Mg/Al ratio. The model with Mg/Al=6 and 20 wt% water content was observed to have a very disordered interlayer arrangement, with preference towards anion-pair arrangements favouring syn-head-to-tail dimer formation. The model with Mg/Al=6 and 30 wt% water content was predicted to exhibit only trans- cis isomerisation.

  10. Use of layered double hydroxides and their derivatives as adsorbents for inorganic and organic pollutants

    NASA Astrophysics Data System (ADS)

    You, Youwen

    Contamination of surface and groundwaters by hazardous inorganic and organic pollutants has become an increasing threat to the safety of drinking waters. Cleanup of contaminated surface and groundwaters has, therefore, become a major focus of environmental research. Primary objectives of this dissertation study were to examine the adsorption properties of layered double hydroxides (LDHs) and their derivatives for inorganic and organic contaminants and to identify potential technologies that utilize LDHs and their derivatives for environment remediation. Studies examined the adsorption characteristics of anionic selenium, arsenic and dicamba (3,6 dichloro-2-methoxy benzoic acid) on original LDHs and calcined-LDHs. Adsorption of selenium and arsenic on LDHs was a function of pH. Competing anions in solution strongly affected adsorption of all three contaminants, with divalent anions decreasing adsorption more intensely than monovalent anions. Adsorbed selenium, arsenic and dicamba could be released from LDHs in anion solutions. Adsorption isotherms for selenium and arsenic retention could be fitted to a simple Langmuir equation. Calcination processes significantly increased adsorption capacities of LDHs. Because of adsorption-desorpion characteristics, LDHs could be recycled. X-ray diffraction patterns revealed an increase of d-spacing coupling with adsorption of contaminants, verifying the intercalation of contaminants into layer structure of LDHs. Long chain anionic surfactants intercalated into LDHs modified their surface properties, resulting in organo-LDHs with hydrophobic surface properties. Various organo-LDHs were developed by incorporating different surfactants into LDHs via different synthesis methods. Surfactant intercalation properties were examined and the geometrical arrangements of the intercalated surfactants were characterized. Results revealed that surfactant molecules could adopt various configurations within the LDH interlayer space. Intercalation

  11. Retention behavior of C1-C6 aliphatic monoamines on anion-exchange and polymethacrylate resins with heptylamine as eluent.

    PubMed

    Ohta, Kazutoku; Ohashi, Masayoshi; Jin, Ji-Ye; Takeuchi, Toyohide; Fujimoto, Chuzo; Choi, Seong-Ho; Ryoo, Jae Jeong; Lee, Kwang-Pill

    2004-06-11

    Retention behavior of C1-C6, aliphatic monoamines (methylamine, ethylamine, propylamine, butylamine, amylamine and hexylamine) on columns (150 mm x 6 mm i.d.) packed with various anion-exchange resins (styrene-divinylbenzene (PS-DVB) copolymer-based strongly basic anion-exchange resin: TSKgel SAX, polymethacrylate-based strongly basic anion-exchange resin: TSKgel SuperQ-5PW and polymethacrylate-based weakly basic anion-exchange resin: TSKgel DEAE-5PW) and unfunctionized polymethacrylate resins (TSKgel G5000PW and TSKgel G3000PWXL) was investigated with basic solutions (sodium hydroxide and heptylamine) as the eluents. Due to strongly electrostatic repulsion (ion-exclusion effect) between these anion-exchange resins and these amines, peak resolution between these amines on these anion-exchange resin columns was unsatisfactory with both sodium hydroxide and heptylamine as the eluents. In contrast, these polymethacrylate resins were successfully applied as the stationary phases for the separation of these C1-C6 amines with heptylamine as eluent, because of both small hydrophobicity and small cation-exchange ability of these resins. Excellent simultaneous separation, highly sensitive conductimetric detection and symmetrical peaks for these C1-C6 amines were achieved on the TSKgel G3000PWXL column in 35 min with 5 mM heptylamine at pH 11.1 as the eluent.

  12. 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.

  13. Elastocapillary-mediated interfacial assembly

    NASA Astrophysics Data System (ADS)

    Evans, Arthur

    2015-11-01

    Particles confined to an interface are present in a large number of industrial applications and ubiquitous in cellular biophysics. Interactions mediated by the interface, such as capillary effects in the presence of surface tension, give rise to rafts and aggregates whose structure is ultimately determined by geometric characteristics of these adsorbed particles. A common strategy for assembling interfacial structures relies on exploiting these interactions by tuning particle anisotropy, either by constructing rigid particles with heterogeneous wetting properties or fabricating particles that have a naturally anisotropic shape. Less explored, however, is the scenario where the interface causes the particles to deform. In this talk I will discuss the implications for interfacial assembly using elastocapillary-mediated interactions. The competition between surface energy and elasticity can wrinkle and buckle adsorbed soft particles, leading to complicated (but programmable) aggregates.

  14. 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.

  15. Mixed metal hydroxides for thickening water or hydrophylic fluids

    SciTech Connect

    Burba, J.L.; Strothers, G.W.

    1991-02-05

    This paper discusses a composition for use as a drilling fluid component. The composition comprises: a liquid having dispersed therein at least one monodispersed monolayer crystalline metal hydroxide conforming essentially to the empirical formula Li{sub m}D{sub d}T(OH)(m + 2d + 3 + na)A{sub a}{sup n}, where D represents divalent metal ions, T represents trivalent metal ions, A represents monovalent or polyvalent anions or negative-valence radicals other than OH{sup {minus}} ions, m is from about zero to about 1, representing the amount of Li ion, d is from about zero to about 4, (m + d) is greater than zero, and na is from about zero to about {minus} 3; and a is an amount of A ions of valence n, where (m + 2d + 3 + na) is equal to or greater than 3 wherein the drilling fluid also contains at least one fluid loss control agent. This patent also describes a drilling fluid component, wherein the drilling fluid also contains at least one fluid loss control agent selected from the group consisting of hydroxyethylcarboxymethyl-cellulose, cornstarch, sodium polyacrylate, starch, polyacrylates, and carboxymethyl-cellulose.

  16. Layered double hydroxide nanoparticles in gene and drug delivery.

    PubMed

    Ladewig, Katharina; Xu, Zhi Ping; Lu, Gao Qing Max

    2009-09-01

    Layered double hydroxides (LDHs) have been known for many decades as catalyst and ceramic precursors, traps for anionic pollutants, catalysts and additives for polymers, but their successful synthesis on the nanometer scale a few years ago opened up a whole new field for their application in nanomedicine. The delivery of drugs and other therapeutic/bioactive molecules (e.g., peptides, proteins, nucleic acids) to mammalian cells is an area of research that is of tremendous importance to medicine and provides manifold applications for any new developments in the area of nanotechnology. Among the many different nanoparticles that have been shown to facilitate gene and/or drug delivery, LDH nanoparticles have attracted particular attention owing to their many desirable properties. This review aims to report recent progress in gene and drug delivery using LDH nanoparticles. It summarizes the advantages and disadvantages of using LDH nanoparticles as carriers for nucleic acids and drugs against the general background of bottlenecks that are encountered by cellular delivery systems. It describes further the models that have been proposed for the internalization of LDH nanoparticles into cells so far and discusses the intracellular fate of the particles and their cargo. The authors offer some remarks on how this field of research will progress in the near future and which challenges need to be overcome before LDH nanoparticles can be used in a clinical setting.

  17. Methotrexate intercalated ZnAl-layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Chakraborty, Manjusha; Dasgupta, Sudip; Soundrapandian, Chidambaram; Chakraborty, Jui; Ghosh, Swapankumar; Mitra, Manoj K.; Basu, Debabrata

    2011-09-01

    The anticancerous drug methotrexate (MTX) has been intercalated into an ZnAl-layered double hydroxide (LDH) using an anion exchange technique to produce LDH-MTX hybrids having particle sizes in the range of 100-300 nm. X-ray diffraction studies revealed increases in the basal spacings of ZnAl-LDH-MTX hybrid on MTX intercalation. This was corroborated by the transmission electron micrographs, which showed an increase in average interlayer spacing from 8.9 Å in pristine LDH to 21.3 Å in LDH-MTX hybrid. Thermogravimetric analyses showed an increase in the decomposition temperature for the MTX molecule in the LDH-MTX hybrid indicating enhanced thermal stability of the drug molecule in the LDH nanovehicle. The cumulative release profile of MTX from ZnAl-LDH-MTX hybrids in phosphate buffer saline (PBS) at pH 7.4 was successfully sustained for 48 h following Rigter-Peppas model release kinetics via diffusion.

  18. 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.

  19. 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

  20. [Calcium hydroxide in the treatment of traumatized teeth].

    PubMed

    Cvek, M

    1989-09-01

    Calcium hydroxide is used in the treatment of different traumatized teeth. New concepts about the effects of calcium hydroxide on vital pulps and immature non vital teeth are developed. Some clinical techniques and their results are described.

  1. 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.

  2. Anion transport and supramolecular medicinal chemistry.

    PubMed

    Gale, Philip A; Davis, Jeffery T; Quesada, Roberto

    2017-04-05

    New approaches to the transmembrane transport of anions are discussed in this review. Advances in the design of small molecule anion carriers are reviewed in addition to advances in the design of synthetic anion channels. The application of anion transporters to the potential future treatment of disease is discussed in the context of recent findings on the selectivity of anion transporters.

  3. 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.

  4. Hydroxide Self-Feeding High-Temperature Alkaline Direct Formate Fuel Cells.

    PubMed

    Li, Yinshi; Sun, Xianda; Feng, Ying

    2017-05-22

    Conventionally, both the thermal degradation of the anion-exchange membrane and the requirement of additional hydroxide for fuel oxidation reaction hinder the development of the high-temperature alkaline direct liquid fuel cells. The present work addresses these two issues by reporting a polybenzimidazole-membrane-based direct formate fuel cell (DFFC). Theoretically, the cell voltage of the high-temperature alkaline DFFC can be as high as 1.45 V at 90 °C. It has been demonstrated that a proof-of-concept alkaline DFFC without adding additional hydroxide yields a peak power density of 20.9 mW cm(-2) , an order of magnitude higher than both alkaline direct ethanol fuel cells and alkaline direct methanol fuel cells, mainly because the hydrolysis of formate provides enough OH(-) ions for formate oxidation reaction. It was also found that this hydroxide self-feeding high-temperature alkaline DFFC shows a stable 100 min constant-current discharge at 90 °C, proving the conceptual feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Rapid mass production of two-dimensional metal oxides and hydroxides via the molten salts method

    NASA Astrophysics Data System (ADS)

    Hu, Zhimi; Xiao, Xu; Jin, Huanyu; Li, Tianqi; Chen, Ming; Liang, Zhun; Guo, Zhengfeng; Li, Jia; Wan, Jun; Huang, Liang; Zhang, Yanrong; Feng, Guang; Zhou, Jun

    2017-05-01

    Because of their exotic electronic properties and abundant active sites, two-dimensional (2D) materials have potential in various fields. Pursuing a general synthesis methodology of 2D materials and advancing it from the laboratory to industry is of great importance. This type of method should be low cost, rapid and highly efficient. Here, we report the high-yield synthesis of 2D metal oxides and hydroxides via a molten salts method. We obtained a high-yield of 2D ion-intercalated metal oxides and hydroxides, such as cation-intercalated manganese oxides (Na0.55Mn2O4.1.5H2O and K0.27MnO2.0.54H2O), cation-intercalated tungsten oxides (Li2WO4 and Na2W4O13), and anion-intercalated metal hydroxides (Zn5(OH)8(NO3)2.2H2O and Cu2(OH)3NO3), with a large lateral size and nanometre thickness in a short time. Using 2D Na2W4O13 as an electrode, a high performance electrochemical supercapacitor is achieved. We anticipate that our method will enable new path to the high-yield synthesis of 2D materials for applications in energy-related fields and beyond.

  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. 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.

  9. Capillary electrophoresis screening of poisonous anions extracted from biological samples.

    PubMed

    Gillette, Robert; Doyle, Janet M; Miller, Mark L; Montgomery, Madeline A; Mushrush, George W

    2006-02-02

    A method was developed for screening human biological samples for poisonous anions using capillary electrophoresis (CE) employing indirect UV detection. The run buffer consisted of 2.25 mM pyromellitic acid, 1.6 mM triethanolamine, 0.75 mM hexamethonium hydroxide and 6.5mM NaOH at pH 7.7. Biological samples were pretreated using solid phase extraction. The method was applied to the analysis of human blood, plasma, urine, and intestinal contents. Twenty-nine different anions were detectable at aqueous concentrations of 1 part per million (ppm) with a typical analysis time less than 20 min. Intraday migration time R.S.D. and peak area R.S.D. for blood samples were less than 1.1% and 6.3%, respectively. Interday migration time R.S.D. for plasma samples ranged from 7.5% to 10.4%. The new method produced efficient separations of various target anions extracted from complex biological matrices.

  10. Structural transformation of nickel hydroxide films during anodic oxidation

    SciTech Connect

    Crocker, Robert W.; Muller, Rolf 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 - 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. 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.

  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, 2010 CFR

    2010-04-01

    ... HUMAN CONSUMPTION (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of... ingredient as generally recognized as safe (GRAS) as a direct human food ingredient is based upon the... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ammonium hydroxide. 184.1139 Section 184.1139...

  14. 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.

  15. 21 CFR 184.1428 - Magnesium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Magnesium hydroxide. 184.1428 Section 184.1428 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific Substances Affirmed as...

  16. 21 CFR 184.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ammonium hydroxide. 184.1139 Section 184.1139 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific Substances Affirmed as...

  17. 21 CFR 184.1763 - Sodium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium hydroxide. 184.1763 Section 184.1763 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific Substances Affirmed as...

  18. 21 CFR 184.1205 - Calcium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Calcium hydroxide. 184.1205 Section 184.1205 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific Substances Affirmed as...

  19. 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.

  20. 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, odorless...

  1. 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, odorless...

  2. 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, odorless...

  3. 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, odorless...

  4. 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, odorless...

  5. 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 for...

  6. 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 for...

  7. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 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...

  8. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 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...

  9. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 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...

  10. 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...

  11. 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...

  12. 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...

  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. Bound Anionic States of Aadenine

    SciTech Connect

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

    2007-03-20

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. 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,wehave 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 newfound 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 new valence states observed here, unlike the dipole-bound state, could exist in condensed phases and might be relevant to radiobiological damage. The discovery of these valence anionic states of adenine was facilitated by the development of (i) an experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (ii) a combinatorial/quantum chemical approach for identification of the most stable tautomers of organic molecules.

  16. Bound Anionic States of Adenine

    SciTech Connect

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

    2007-03-20

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. 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 newfound 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 new valence states observed here, unlike the dipole-bound state, could exist in condensed phases and might be relevant to radiobiological damage. The discovery of these valence anionic states of adenine was facilitated by the development of (i) an experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (it) a combinatorial/quantum chemical approach for identification of the most stable tautomers of organic molecules.

  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. 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.

  19. 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.

  20. Anion selectivity in biological systems.

    PubMed

    Wright, E M; Diamond, J M

    1977-01-01

    As background for appreciating the still-unsolved problems of monovalent anion selectivity, we summarize the facts and intepretations that seem reasonably well established. In section II we saw that specific effects of monovalent anions on biological and physical systems define qualitative patterns, in that only certain sequences of anion effects are observed. For example, the 4 halides can be permitted on paper as 4! = 24 sequences, yet only 5 of these sequences have been observed in nature as potency sequences. In addition, there are quantitative regularities in anion potency that permit the construction of so-called empirical selectivity isotherms (Figs. 4 and 13). That is, a given potency sequence is found to be associated with only a certain modest range of selectivity ratios. The sequences and isotherms apply to effects with a nonequilibrium component (e.g., permeability and conductance sequences) as well as to purely equilibrium effects. Since students of cation selectivity have had difficulty accepting this conclusion, we discuss the reasons why it is not as paradoxical as it at first seems. In sections III and IV we develop four theoretical models to account for the observed anion potency sequences as sequences of equilibrium binding energies. Two of these models involve calculation of electrostatic binding energies between anions and monopolar or dipolar cationic sites, assuming anions as well as sites to be rigid and nonpolarizable. The other two models use thermochemically measured binding energies between anions and thealkali cations or occasionally alkaline-earth cations, which in fact approximate rigid, nonpolarizable spheres. All four models consider the anion selectivity pattern of a given cationic site to be determined by anion differences in the balance between hydration energies and ion-site binding energies. Site differences in anion selectivity pattern are attributed to site differences in radius, charge, coordination number, or dipole length

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Target delivery and controlled release of the chemopreventive drug sulindac by using an advanced layered double hydroxide nanomatrix formulation system.

    PubMed

    Minagawa, Keiji; Berber, Mohamed R; Hafez, Inas H; Mori, Takeshi; Tanaka, Masami

    2012-04-01

    Target delivery and controlled release of the chemopreventive drug sulindac that possesses low water solubility present a great challenge for its pharmaceutical industry. Here, we offered an advanced nanomatrix formulation system of sulindac based on layered double hydroxide materials. The X-ray analysis and infrared spectroscopy confirmed the incorporation of sulindac into the gallery of the layered double hydroxides. The incorporation ratios of sulindac were recorded to be 45, 31 and 20 for coprecipitation, anion-exchange and reconstruction techniques, respectively. The scanning electron microscopy showed a nanomatrix-structure of ~50 nm. The release studies of sulindac-nanomatrix showed a 96% controlled release at the small intestine solution during 3 h(s), indicating an enhancement in the dissolution profile of sulindac after the matrix formation. The layered structure of the matrix supplied sulindac with a well-ordered structure and a relatively hydrophobic microenvironment that controlled the guest hydrolysis and reactivity during the release process. The laminar structure of layered double hydroxides offered a safe preservation for sulindac against photodecarboxylation, and enhanced the drug thermal stability from 190 to 230° C. The ionic electrostatic interaction of sulindac through its acidic group with layered double hydroxides demolished the gastrointestinal ulceration.

  8. 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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Evaluation of various concentrations of alkaline surface treatment on interfacial bond strengths of amalgam bonded to amalgam.

    PubMed

    Mirza, Asaad Javaid; Ahmad, Asif; Mohammad, Taqi; Khan, Zahid Akhter

    2013-09-01

    This study was done to assess the influence of alkaline surface modification on interfacial bond strength of existing fractured (old) amalgam restoration bonded to fresh amalgam. Old and Fresh amalgam interfaced samples were prepared by applying a 4-methacryloyloxyethy trimellitate anhydride (4-META) containing adhesive. The adhesive used was Amalgabond (Parkell, Farmingdale, NY 11735, USA). Four concentrations of calcium hydroxide Ca(OH)2 solutions were used as a surface modifiers for old amalgam to increase the pH of the amalgam surfaces. The concentrations used were 2.5, 5, 10 and 15%. Direct measurement of the interfacial bond strength was carried out using an electromechanical universal tensile testing machine at crosshead speed of 10mm per minute. Results show that all the calcium hydroxide modified samples produced the increased tensile bond strength (TBS) as compared to their control group. The highest values of bond strength were achieved using 15% Ca(OH)2 solution as surface modifier. Pretreatment of fractured amalgam with calcium hydroxide improves the bond strength of 4-META adhesives. Its use in repair of amalgam may therefore be considered.

  10. Preparation and characterization of an anti-inflammatory agent based on a zinc-layered hydroxide-salicylate nanohybrid and its effect on viability of Vero-3 cells

    PubMed Central

    Ramli, Munirah; Hussein, Mohd Zobir; Yusoff, Khatijah

    2013-01-01

    A new organic-inorganic nanohybrid based on zinc-layered hydroxide intercalated with an anti-inflammatory agent was synthesized through direct reaction of salicylic acid at various concentrations with commercially available zinc oxide. The basal spacing of the pure phase nanohybrid was 15.73 Å, with the salicylate anions arranged in a monolayer form and an angle of 57 degrees between the zinc-layered hydroxide interlayers. Fourier transform infrared study further confirmed intercalation of salicylate into the interlayers of zinc-layered hydroxide. The loading of salicylate in the nanohybrid was estimated to be around 29.66%, and the nanohybrid exhibited the properties of a mesoporous-type material, with greatly enhanced thermal stability of the salicylate compared with its free counterpart. In vitro cytotoxicity assay revealed that free salicylic acid, pure zinc oxide, and the nanohybrid have a mild effect on viability of African green monkey kidney (Vero-3) cells. PMID:23345976

  11. Nickel-cobalt alloy nanosheets obtained from reductive hydrothermal-treatment of nickel-cobalt hydroxide carbonate

    SciTech Connect

    Ghotbi, Mohammad Yeganeh; Jolagah, Ali; Afrasiabi, Hasan-ali

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer An anionic layered material, nickel-cobalt hydroxide carbonate was synthesized. Black-Right-Pointing-Pointer Reductive hydrothermal-treatment of the layered precursor produced an alloy. Black-Right-Pointing-Pointer The alloy is a bimetallic nanostructured nickel-cobalt and a soft magnet material. -- Abstract: Nickel-cobalt hydroxide carbonate, a layered material was synthesized by the co-precipitation method using urea as precipitant agent. This anionic layered material with hexagonal structure is constructed from nickel and cobalt ions within the layers and carbonate anions between the layers. Nickel-cobalt alloy with pure cubic phase was obtained by a reductive hydrothermal-treatment of the layered precursor. Powder X-ray diffraction pattern and Fourier transform infrared spectroscopy confirmed the formation of the initial layered material and its metallic alloy product. That is, the nickel-cobalt alloy has really produced via a wet chemical route for the first time. Magnetic measurement revealed that the alloy sample is a soft magnet material.

  12. Interfacial ionic 'liquids': connecting static and dynamic structures

    DOE PAGES

    Uysal, Ahmet; Zhou, Hua; Feng, Guang; ...

    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. For this research, 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. Lastly, 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. The results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (~0.15 eV).« less

  13. 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 G.; 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. For this research, 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. Lastly, 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. The results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (~0.15 eV).

  14. Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Lam, Royce K.; Smith, Jacob W.; Rizzuto, Anthony M.; Karslıoǧlu, Osman; Bluhm, Hendrik; Saykally, Richard J.

    2017-03-01

    The fractionation of ions at liquid interfaces and its effects on the interfacial structure are of vital importance in many scientific fields. Of particular interest is the aqueous carbonate system, which governs both the terrestrial carbon cycle and physiological respiration systems. We have investigated the relative fractionation of carbonate, bicarbonate, and carbonic acid at the liquid/vapor interface finding that both carbonate (CO32-) and carbonic acid (H2CO3) are present in higher concentrations than bicarbonate (HCO3-) in the interfacial region. While the interfacial enhancement of a neutral acid relative to a charged ion is expected, the enhancement of doubly charged, strongly hydrated carbonate anion over the singly charged, less strongly hydrated bicarbonate ion is surprising. As vibrational sum frequency generation experiments have concluded that both carbonate and bicarbonate anions are largely excluded from the air/water interface, the present results suggest that there exists a significant accumulation of carbonate below the depletion region outside of the area probed by sum frequency generation.

  15. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Anion transporters and biological systems.

    PubMed

    Gale, Philip A; Pérez-Tomás, Ricardo; Quesada, Roberto

    2013-12-17

    In this Account, we discuss the development of new lipid bilayer anion transporters based on the structure of anionophoric natural products (the prodigiosins) and purely synthetic supramolecular systems. We have studied the interaction of these compounds with human cancer cell lines, and, in general, the most active anion transporter compounds possess the greatest anti-cancer properties. Initially, we describe the anion transport properties of synthetic molecules that are based on the structure of the family of natural products known as the prodiginines. Obatoclax, for example, is a prodiginine derivative with an indole ring that is currently in clinical trials for use as an anti-cancer drug. The anion transport properties of the compounds were correlated with their toxicity toward small cell human lung cancer GLC4 cells. We studied related compounds with enamine moieties, tambjamines, that serve as active transporters. These molecules and others in this series could depolarize acidic compartments within GLC4 cells and trigger apoptosis. In a study of the variation of lipophilicity of a series of these compounds, we observed that, as log P increases, the anion transport efficiency reaches a peak and then decreases. In addition, we discuss the anion transport properties of series of synthetic supramolecular anion receptor species. We synthesized trisureas and thioureas based on the tren backbone, and found that the thiourea compounds effectively transport anions. Fluorination of the pendant phenyl groups in this series of compounds greatly enhances the transport properties. Similar to our earlier results, the most active anion transporters reduced the viability of human cancer cell lines by depolarizing acidic compartments in GLC4 cells and triggering apoptosis. In an attempt to produce simpler transporters that obey Lipinski's Rule of Five, we synthesized simpler systems containing a single urea or thiourea group. Once again the thiourea systems, and in particular

  17. Molecular modeling of the structure and dynamics of the interlayer species of ZnAlCl layered double hydroxide.

    PubMed

    Pisson, J; Morel, J P; Morel-Desrosiers, N; Taviot-Guého, C; Malfreyt, P

    2008-07-03

    Molecular dynamics simulations of the ZnAl layered double hydroxide containing interlayer chloride anions have been performed in the NpT and Np(zz)T statistical ensembles for metal Zn/Al ratios of 2 and 3. We have monitored the interlayer spacing as a function of the number of intercalated water molecules for each statistical ensemble. We have studied how these profiles are affected by the method of calculation of the charges of the hydroxide layer atoms. Diffusion coefficients of the interlayer water molecules have been calculated for different Zn/Al ratios. The calculation of the chemical potential of the interlayer water molecules has been carried out for three amounts of interlayer water molecules. The calculation showed a qualitative agreement with the bulk water chemical potential within a range of interlayer water molecule contents.

  18. 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.

  19. SEM Analysis of the Interfacial Transition Zone between Cement-Glass Powder Paste and Aggregate of Mortar under Microwave Curing

    PubMed Central

    Kong, Yaning; Wang, Peiming; Liu, Shuhua; Zhao, Guorong; Peng, Yu

    2016-01-01

    In order to investigate the effects of microwave curing on the microstructure of the interfacial transition zone of mortar prepared with a composite binder containing glass powder and to explain the mechanism of microwave curing on the improvement of compressive strength, in this study, the compressive strength of mortar under microwave curing was compared against mortar cured using (a) normal curing at 20 ± 1 °C with relative humidity (RH) > 90%; (b) steam curing at 40 °C for 10 h; and (c) steam curing at 80 °C for 4 h. The microstructure of the interfacial transition zone of mortar under the four curing regimes was analyzed by Scanning electron microscopy (SEM). The results showed that the improvement of the compressive strength of mortar under microwave curing can be attributed to the amelioration of the microstructure of the interfacial transition zone. The hydration degree of cement is accelerated by the thermal effect of microwave curing and Na+ partially dissolved from the fine glass powder to form more reticular calcium silicate hydrate, which connects the aggregate, calcium hydroxide, and non-hydrated cement and glass powder into a denser integral structure. In addition, a more stable triangular structure of calcium hydroxide contributes to the improvement of compressive strength. PMID:28773854

  20. A new paradigm for anion trapping in high capacity and selectivity: crystal-to-crystal transformation of cationic materials.

    PubMed

    Fei, Honghan; Bresler, Marc R; Oliver, Scott R J

    2011-07-27

    We describe a new methodology to the selective trapping of priority pollutants that occur inherently as oxo-anions (e.g., perchlorate, chromate, arsenate, pertechnetate, etc.) or organic anions (e.g., salicylate, pharmaceuticals, and their metabolites, which are often chlorinated into potentially more harmful compounds). The typical approach to trapping anions is exchange into cationic hosts such as resins or layered double hydroxides. Both capacity and selectivity are limited by the equilibrium of the process and moreover are often subject to interference, e.g. by carbonate that is always present in water from atmospheric CO(2). Our approach takes advantage of the metastability of our cationically charged materials to instead trap by recrystallization to a new structure. Exceptionally high adsorption capacities for permanganate and perrhenate--studied as models for pertechnetate--were found for a Ag(I)-based cationic extended framework. The exchange capacity reached 292 and 602 mg/g, respectively, over five times the exchange capacity compared to conventional layered double hydroxides. Our cationic material can also selectively trap these and other toxic oxo-anions when nontoxic anions (e.g., nitrate, carbonate) were present in an over 100-fold excess concentration.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Influence of nature of precursors on the formation and structure of Cu Ni Cr mixed oxides from layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Zhang, Lihong; Zhu, Jia; Jiang, Xiaorui; Evans, David G.; Li, Feng

    2006-08-01

    Analogous layered double hydroxides (LDHs) with the Cu2+/Ni2+/Cr3+ molar ratio of 1/2/1 on the brucite-like layers and interlayer anions (viz sulfate, nitrate and carbonate, respectively) were synthesized by a coprecipitation method. For the first time, the effects of interlayer anions on the structural properties of as-synthesized LDHs and resulting calcined products at 773 K were investigated by means of powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), simultaneous thermogravimetric and differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR). The results indicate that the nature of interlayer anions involved within the hydrotalcite (HT)-like structure has a larger influence on the thermal stability of LDHs precursors. Calcination of well-crystallized LDHs leads to the formation of mixed metal oxides including CuO, NiO and Cu2+-, Ni2+- and Cr3+-containing spinel phases, the composition distributions of which obtained from LDHs precursors depend on the nature of interlayer anions, thus resulting in the difference of the reducibility of reducible metal species in the calcined LDHs. Moreover, the surface basicity of the calcined material, which is related to the different behaviour of LDHs precursors during the thermal decomposition depending on the interlayer anions, increases progressively following the order of calcined LDHs from sulfate to nitrate and carbonate.

  6. Layered double hydroxide intercalated with p-methylbenzoate and p-bromobenzoate: molecular simulations and XRD analysis.

    PubMed

    Kovár, Petr; Melánová, Klára; Zima, Vítezslav; Benes, Ludvík; Capková, Pavla

    2008-03-01

    Samples of Mg4Al2 layered double hydroxide (LDH) intercalated with p-methylbenzoate and p-bromobenzoate anions were prepared by reconstruction of calcined LDH. The interlayer arrangement of guests was investigated by molecular modeling combined with X-ray powder diffraction and thermogravimetry. Molecular modeling was carried out in a Cerius2 modeling environment. In both structures the guest anions adopt a nearly perpendicular arrangement of their long axis with respect to the host layers and they are anchored to the OH groups of the layers through COO* groups via electrostatic interactions. Molecular modeling revealed that both structures of the intercalates exhibit a certain disorder of guest anions in the interlayer space. In the case of LDH-p-methylbenzoate intercalate the anions tend to be situated in disordered rows, and the LDH-p-bromobenzoate intercalate exhibits a total disorientation of guest anions. A good agreement between calculated and measured X-ray diffraction patterns and between experimental and calculated basal spacings was obtained. In the LDH-p-methylbenzoate intercalate d exp=16.96 A and d calc=16.97 A, and in the case of LDH-p-bromobenzoate intercalate d exp=17.19 A and d calc=17.40 A.

  7. Particle size and shape of calcium hydroxide

    PubMed Central

    Komabayashi, Takashi; D’souza, Rena N; Dechow, Paul C; Safavi, Kamran E.; Spångberg, Larz S.W.

    2009-01-01

    The aim of this study was to examine the particle length, width, perimeter, and aspect ratio of calcium hydroxide powder using a flow particle image analyzer (FPIA). Five sample groups each with 10mg calcium hydroxide were mixed with 15mL of alcohol and sonicated. Digital images of the particle samples were taken using the FPIA and analyzed with a one-way ANOVA. The overall averages±S.D. among the five groups for particle length (μm), width (μm), perimeter (μm), and aspect ratio were 2.255±1.994, 1.620±1.464, 6.699±5.598, and 0.737±0.149, respectively. No statistical significance was observed among the groups for all parameters. When the total of 46,818 particles from all five groups were classified into the five length categories of 0.5μm increments, there were significant differences in width, perimeter, and aspect ratio (all p-values<0.0001). In conclusion, calcium hydroxide particles have a size and shape that may allow direct penetration into open dentin tubules. PMID:19166791

  8. Hydroxide catalysis bonding for astronomical instruments

    NASA Astrophysics Data System (ADS)

    van Veggel, Anna-Maria A.; Killow, Christian J.

    2014-06-01

    Hydroxide catalysis bonding (HCB) as a jointing technique has been under development for astronomical applications since ˜1998 (patented by D.-H. Gwo). It uses an aqueous hydroxide solution to form a chemical bond between oxide or oxidisable materials (e.g., SiO2, sapphire, silicon and SiC). It forms strong, extremely thin bonds, and is suitable for room temperature bonding, precision alignment, operation in ultra-low vacuum and down to temperatures of 2.5 K. It has been applied in the NASA satellite mission Gravity Probe B and in the ground-based gravitational wave (GW) detector GEO600. It will soon fly again on the ESA LISA Pathfinder mission and is currently being implemented in the Advanced LIGO and Virgo ground-based GW detectors. This technique is also of considerable interest for use in other astronomical fields and indeed more broadly, due to its desirable, and adjustable, combination of properties. This paper gives an overview of how HCB has been and can be applied in astronomical instruments, including an overview of the current literature on the properties of hydroxide catalysis bonds.

  9. 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.

  10. 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.

  11. Methotrexate intercalated layered double hydroxides with different particle sizes: structural study and controlled release properties.

    PubMed

    Zhang, Xiao-Qing; Zeng, Mei-Gui; Li, Shu-Ping; Li, Xiao-Dong

    2014-05-01

    To study the influence of particle size on release properties, drug efficacy and other properties, a series of methotrexate intercalated layered double hydroxides (MTX/LDHs) nanohybrids with different particle sizes were synthesized through traditional coprecipitation method, by using the mixture of water and polyethylene glycol (volume ratio is 3:1) as solvent. The relationship between particle size and hydrothermal treatment conditions (i.e., time and temperature) had been systematically investigated, and the results indicate that the particle size can be precisely controlled between 70 and 300 nm. Elemental C/H/N and inductive coupled plasma (ICP) analysis indicated that different hydrothermal treatment almost has no effect on compositions of the nanohybrids. X-ray diffraction (XRD) patterns and fourier transform infrared spectroscopy (FTIR) investigations manifested the successful intercalation of MTX anions. MTX/LDHs particles exhibited hexagonal platelet morphology with round corner, due to the adsorption of MTX anions on positively charged LDHs surface. In addition, the crystallinity of MTX/LDHs increased with the particle diameters and the thermal stability of MTX anions was enhanced by holding together with LDHs layers. The in vitro release showed that bigger particles have much longer release duration, and the bioassay tests indicated that bigger particles are more efficient in the suppression of the tumor cells.

  12. Removal of Remazol Blue 19 from wastewater by zinc-aluminium-chloride-layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Elkhattabi, El Hassan; Lakraimi, Mohamed; Badreddine, Mohamed; Legrouri, Ahmed; Cherkaoui, Omar; Berraho, Moha

    2013-06-01

    Layered double hydroxides (LDHs), also called anionic clays, consist of cationic brucite-like layers and exchangeable interlayer anions. These hydrotalcite-like compounds, with Zn and Al in the layers and chloride in the interlayer space, were prepared following the coprecipitation method at constant pH. The affinity of this material for Remazol Blue 19, RB19 [ 2- (3- (4- Amino- 9,10- dihydro- 3- sulpho- 9,10- dioxoanthracen- 4- yl) aminobenzenesulphonyl) vinyl) disodiumsulphate], was studied as a function of contact time, pH of the solutions LDH dose and the RB19/[Zn-Al-Cl] mass ratio. It was found that 48 h is enough time for the equilibrium state to be reached with maximum RB19 retention at pH of 9 for an LDH dose equal to 100 mg and with an RB19/[Zn-Al-Cl] mass ratio higher than 3. The adsorption isotherm, described by the Langmuir model, is of L-type. The results demonstrate that RB19 retention on LDHs occurs by adsorption on external surface when RB19/[Zn-Al-Cl] mass ratio is equal or <3 and by both adsorption and interlayer ion exchange for ratios higher than 3. A mechanism for removal of RB19 anion has been confirmed by X-ray diffraction, IR spectroscopy and TG analysis (TG and DTG curves).

  13. Layered double hydroxides as supports for intercalation and sustained release of antihypertensive drugs

    NASA Astrophysics Data System (ADS)

    Xia, Sheng-Jie; Ni, Zhe-Ming; Xu, Qian; Hu, Bao-Xiang; Hu, Jun

    2008-10-01

    Zn/Al layered double hydroxides (LDHs) were intercalated with the anionic antihypertensive drugs Enalpril, Lisinopril, Captopril and Ramipril by using coprecipitation or ion-exchange technique. TG-MS analyses suggested that the thermal stability of Ena -, Lis - (arranged with monolayer, resulted from X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) analysis was enhanced much more than Cap - and Ram - (arranged with bilayer). The release studies show that the release rate of all samples markedly decreased in both pH 4.25 and 7.45. However, the release time of Ena -, Lis - were much longer compared with Cap -, Ram - in both pH 4.25 and 7.45, it is possible that the intercalated guests, arranged with monolayer in the interlayer, show lesser repulsive force and strong affinity with the LDH layers. And the release data followed both the Higuchi-square-root law and the first-order equation well. Based on the analysis of batch release, intercalated structural models as well as the TG-DTA results, we conclude that for drug-LDH, stronger the affinity between intercalated anions and the layers is, better the thermal property and the stability to the acid attack of drug-LDH, and the intercalated anions are easier apt to monolayer arrangement within the interlayer, were presented.

  14. Anion Binding in Self-Assembled Monolayers in Mesoporous Supports (SAMMS)

    SciTech Connect

    Mattigod, Shas V.; Fryxell, Glen E.; Parker, Kent E.

    2007-02-19

    The binding of various anions to cationic transition metal complexes lining the pores of mesoporous silica is characterized and correlated to anion basicity. By lining the pore surfaces of mesoporous silica with self-assembled monolayer of organosilanes terminated with chemically selective ligands, a powerful new class of heavy metal sorbents has been realized, called self-assembled monolayers on mesoporous supports (SAMMS) [1-18]. When this interfacial functionality is composed of cationic transition metal complexes, a valuable new class of anion exchange material came into being [19]. Yoshitake and co-workers, have extended this concept to include other transition metal cations in similar cationic complexes inside mesoporous silica [20-23]. Other amine-based ligands (including polymer-based systems) were also explored, and the highest binding capacity was found with the diethylenetriamine ligand [20]. This synthetic strategy allows the chemist to easily modify both the metal center and ligand field, thereby tailoring chemical selectivity at multiple levels.

  15. Empirical electronic polarizabilities in oxides, hydroxides, oxyfluorides, and oxychlorides

    NASA Astrophysics Data System (ADS)

    Shannon, Robert D.; Fischer, Reinhard X.

    2006-06-01

    An extensive set of infinite-wavelength refractive indices recently derived from a single-oscillator Sellmeier equation [J. Phys. Chem. Ref. Data 31, 931 (2002)] was used to obtain mean total polarizabilities for 340 oxides, 3 hydroxides, 46 oxyhydroxides, 10 oxyfluorides, 8 oxychlorides, 80 hydrates, and 51 fluorides. These data, in conjunction with the polarizability additivity rule and a least-squares procedure, were used to obtain electronic polarizabilities for 79 cations, H2O , and 4 anions (F-,Cl-,OH-,O2-) . Using literature values for free-cation polarizabilities, neglecting cation coordination, and allowing the variation of anion polarizability according to logα-=logα-o-No/Van2/3 where α-= anion polarizability, α-o= empirical free-anion polarizability, Van= anion molar volume and No= a constant, the refinement gives agreement (±5%) in only 92 out of 381 total mean polarizabilities of 252 compounds. Varying cation polarizabilities, but still neglecting dependencies on cation coordination numbers (CN), allowed us to reproduce total polarizability values to within 5% for 611 out of 650 data on 487 oxides, hydrates, oxyfluorides, and oxychlorides. In the next stage we modified a light-scattering (LS) model by Jemmer [J. Phys. Chem. A 102, 8377 (1998)] to give the expression α(CN,R)=[a1+a2CNcae-a3R]-1 , where CNca= the number of nearest-neighbor ions (cation-anion interactions); R= cation-anion interatomic distance; and a1 , a2 , and a3 are constants. This expression provides for a smooth decrease in polarizability at low CN’s to the free-cation value at infinite CN’s (R=∞) . Fitting polarizability values for Mg, Ca, Sr, Ba, Pb, Y, and La to this relationship provided a fit to within 5% of 601 out of 650 data. The final step in the refinement process, which used 534 total polarizabilities from 387 compounds, excluded compounds with (1) sterically strained (SS) structures, (2) corner-shared octahedral (CSO) network and chain structures such as

  16. Liquefaction of Douglas Fir wood slurries: titration of acids and anions in aqueous product and feed slurries

    SciTech Connect

    Davis, H.G.

    1981-03-01

    After hydrolytic pretreatment, wood slurries contain substantial amounts of organic acids. Additional acids are produced during the liquefaction step whether or not there is prehydrolysis. The acids have pH's in the range of about 3 to 5 and are easily titrated potentiometrically with sodium hydroxide. Anions present in neutralized slurry or in aqueous product can be titrated with hydrogen chloride solution with appropriate corrections for sulfate if present, and for excess titrant at the low pH of the endpoint.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Interfacial behavior of simple inorganic salts at the air-water interface investigated with a polarizable model with electrostatic damping.

    PubMed

    Cummings, Oneka T; Wick, Collin D

    2013-08-14

    New molecular models that incorporated polarizable interactions with electrostatic damping were developed to better understand the interfacial properties of aqueous electrolyte systems. The models were parameterized to give free energies of aqueous solvation and the change in activity with respect to concentration in agreement with experiment. Specifically, we investigated NaCl, NaBr, and NaI systems, finding anion propensity for the air-water interface was reduced in comparison with previously developed polarizable models. This coincided with a more negative surface excess than that given by previously developed polarizable models. Furthermore, we investigated the interfacial properties of SrCl2 aqueous systems, finding that strontium had a moderate enhancement in interfacial density in comparison with bulk, while still having a fairly large negative surface excess, in agreement with experimental results.

  3. 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

  4. 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

    2013-05-02

    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.

  5. Physical properties of fixed-charge layer double hydroxides

    NASA Astrophysics Data System (ADS)

    Hines, D. R.; Solin, S. A.; Costantino, Umberto; Nocchetti, Morena

    2000-05-01

    The physical properties of a series of layer double hydroxides (LDH) of the form [(CO3)0.195(1-x)Cl0.39x(H2O)y]:[Zn0.61Al0.39(OH)2], 0<=x<=1, 0<=y<=(0.4+0.2x) have been studied. The hydration dynamics of these materials indicate that the guest layer water molecules form a hydration ring which defines the height of the solvated, nested Cl anion. The water molecules can tilt around their C2v axis such that the height of the solvated Cl ion is a function of the number of molecules forming the hydration ring. The composition dependence of the basal spacing, determined from x-ray-diffraction powder patterns measured as a function of humidity and temperature for these materials, is a function of both the Cl concentration (x) and the number of guest layer water molecules (y). Distinct basal spacing curves are observed for fully hydrated, partially hydrated, and dehydrated materials. At x=1 the Cl end-member material exhibits a change in stacking sequence from a 3R polytype to a 2H polytype upon dehydration. The dehydrated form of this material also exhibits a (3×3)R30° superlattice ordering of the Cl ions. Due to the nesting of the Cl ion and the active nature of the water molecules, the basal spacing vs x curve for the dehydrated materials is the only curve that can be fit by the discrete finite layer rigidity model. The interlayer rigidity parameter for LDH materials has been determined to be p=4.84+/-0.06 indicating that these materials are stiffer than class-II layered solids but not as stiff as class-III layered solids.

  6. Hydrogen in anion vacancies of semiconductors

    SciTech Connect

    Du, Mao-Hua; Singh, David J

    2009-01-01

    Density functional calculations show that, depending on the anion size, hydrogen in anion vacancies of various II-VI semiconductors can be either two-fold or four-fold coordinated, and has either amphoteric or shallow donor character. In general, the multi-coordination of hydrogen in an anion vacancy is the indication of an anionic H, H { ion, in the relatively ionic environment. In more covalent semiconductors, H would form a single cation-H bond in the anion vacancy.

  7. 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.

  8. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Kinetics of Polymer Interfacial Reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Shuo; Koberstein, Jeffrey

    2012-02-01

    Germanium crystals modified with high quality azide functional monolayers are used to directly monitor in situ the kinetics of interfacial ``click'' reactions with complementary alkyne end-functional poly(n-butyl acrylate) (PnBA) and polystyrene (PS) by attenuated total reflectance infrared spectroscopy (ATR-IR). In the presence of copper (I), the azide-modified Ge substrates react quantitatively with PnBA and PS via a 1,3-dipolar cycloaddition reaction. Time-resolved ATR-IR measurements show two regimes of kinetic behavior, as predicted by theory. In the first regime the rate is rapid and is controlled by diffusion of the polymer through the solvent, scaling with the square root of time. The rate slows considerably in the second regime, limited by penetration of the reacting polymer through the covalently bound polymer brush layer, scaling with the natural logarithm of time. The influence of polymer size and solvent quality are reported.

  10. 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.

  11. 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.

  12. Antimicrobial Activity of Calcium Hydroxide in Endodontics: A Review

    PubMed Central

    Shalavi, S; Yazdizadeh, M

    2012-01-01

    The purpose of endodontic therapy is to preserve the patient's natural teeth without compromising the patient's local or systemic health. Calcium hydroxide has been included in several materials and antimicrobial formulations that are used in several treatment modalities in endodontics, such as inter-appointment intracanal medicaments. The purpose of this article was to review the antimicrobial properties of calcium hydroxide in endodontics. Calcium hydroxide has a high pH (approximately 12.5-12.8) and is classified chemically as a strong base. The lethal effects of calcium hydroxide on bacterial cells are probably due to protein denaturation and damage to DNA and cytoplasmic membranes. Calcium hydroxide has a wide range of antimicrobial activity against common endodontic pathogens but is less effective against Enterococcus faecalis and Candida albicans. Calcium hydroxide is also a valuable anti-endotoxin agent. However, its effect on microbial biofilms is controversial. PMID:23323217

  13. Organic anion uptake by hepatocytes.

    PubMed

    Wolkoff, Allan W

    2014-10-01

    Many of the compounds taken up by the liver are organic anions that circulate tightly bound to protein carriers such as albumin. The fenestrated sinusoidal endothelium of the liver permits these compounds to have access to hepatocytes. Studies to characterize hepatic uptake of organic anions through kinetic analyses, suggested that it was carrier-mediated. Attempts to identify specific transporters by biochemical approaches were largely unsuccessful and were replaced by studies that utilized expression cloning. These studies led to identification of the organic anion transport proteins (oatps), a family of 12 transmembrane domain glycoproteins that have broad and often overlapping substrate specificities. The oatps mediate Na(+)-independent organic anion uptake. Other studies identified a seven transmembrane domain glycoprotein, Na(+)/taurocholate transporting protein (ntcp) as mediating Na(+)-dependent uptake of bile acids as well as other organic anions. Although mutations or deficiencies of specific members of the oatp family have been associated with transport abnormalities, there have been no such reports for ntcp, and its physiologic role remains to be determined, although expression of ntcp in vitro recapitulates the characteristics of Na(+)-dependent bile acid transport that is seen in vivo. Both ntcp and oatps traffic between the cell surface and intracellular vesicular pools. These vesicles move through the cell on microtubules, using the microtubule based motors dynein and kinesins. Factors that regulate this motility are under study and may provide a unique mechanism that can alter the plasma membrane content of these transporters and consequently their accessibility to circulating ligands.

  14. Organic Anion Uptake by Hepatocytes

    PubMed Central

    Wolkoff, Allan W.

    2016-01-01

    Many of the compounds taken up by the liver are organic anions that circulate tightly bound to protein carriers such as albumin. The fenestrated sinusoidal endothelium of the liver permits these compounds to have access to hepatocytes. Studies to characterize hepatic uptake of organic anions through kinetic analyses, suggested that it was carrier-mediated. Attempts to identify specific transporters by biochemical approaches were largely unsuccessful and were replaced by studies that utilized expression cloning. These studies led to identification of the organic anion transport proteins (oatps), a family of 12 transmembrane domain glycoproteins that have broad and often overlapping substrate specificities. The oatps mediate Na+-independent organic anion uptake. Other studies identified a seven transmembrane domain glycoprotein, Na+/taurocholate transporting protein (ntcp) as mediating Na+-dependent uptake of bile acids as well as other organic anions. Although mutations or deficiencies of specific members of the oatp family have been associated with transport abnormalities, there have been no such reports for ntcp, and its physiologic role remains to be determined, although expression of ntcp in vitro recapitulates the characteristics of Na+-dependent bile acid transport that is seen in vivo. Both ntcp and oatps traffic between the cell surface and intracellular vesicular pools. These vesicles move through the cell on microtubules, using the microtubule based motors dynein and kinesins. Factors that regulate this motility are under study and may provide a unique mechanism that can alter the plasma membrane content of these transporters and consequently their accessibility to circulating ligands. PMID:25428858

  15. Simultaneous Enhancements of Conductivity and Stability for Anion Exchange Membranes (AEMs) through Precise Structure Design

    PubMed Central

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

    2014-01-01

    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 ioinc 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 convinient 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. PMID:25255843

  16. Chemical stability of hydroxysulphate green rust synthetised in the presence of foreign anions: carbonate, phosphate and silicate

    NASA Astrophysics Data System (ADS)

    Ruby, C.; Géhin, A.; Aissa, R.; Ghanbaja, J.; Abdelmoula, M.; Génin, J.-M. R.

    2006-01-01

    Hydroxysulphate green rust {left\\{ {{text{GR}}{left( {{text{SO}}^{{2 - }}4 } right)}} right\\}} species were precipitated in the presence of various anions. {text{GR}}{left( {{text{SO}}^{{2 - }}4 } right)} is stable at ˜pH 7 and is transformed into a mixture of magnetite and ferrous hydroxide when the pH raised at ˜12. In the presence of carbonate species, {text{GR}}{left( {{text{SO}}^{{2 - }}4 } right)} is partially transformed into a mixture of magnetite and siderite at ˜pH 8.5. This transformation is stopped when silicate anions are present in the solution. As already observed for phosphate anions, the adsorption of silicate anions on the lateral faces of the {text{GR}}{left( {{text{SO}}^{{2 - }}4 } right)} crystals may explain this stabilization effect. Sulphate anions are easily exchanged by carbonate species at ˜pH 10.5. In contrast, anionic exchange between sulphate and phosphate anions was not observed.

  17. 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.

  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. Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

    SciTech Connect

    Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon; Ocola, Leonidas E.; Nealey, Paul F.

    2016-03-08

    Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which are anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.

  20. Anionic Gemini Surfactants:. Synthesis and Surface Active Properties

    NASA Astrophysics Data System (ADS)

    Shukla, Dipti; Tyagi, V. K.

    New compounds bearing two phosphate groups and two long chain (dodecyl) were prepared by two-step reaction: (i) phosphorylation of dodecanol with pyrophosphoric acid, (ii) reaction of dodecyl phosphate with N(CH3)4OH and 1,6-dibromo hexane. The effect of reaction variables like time and molar ratio of reactants on yield has also been reported. The 1:2:0.5 molar ratio of reactants (dodecyl phosphate, N(CH3)4OH, and Br(CH2)6 Br, respectively) and 3 h duration resulted to give maximum yield of anionic gemini surfactants. The structure of synthesized surfactant was investigated by modern analytical techniques, viz. FT-IR, 1H NMR, 13C NMR. Amphipathic disodium phosphates were obtained by neutralization of free acids with sodium hydroxide and their surface active properties in aqueous solution were measured. These disodium phosphates possessed 77.3% anionic content and showed good water solubility. Foaming properties and wetting ability were also evaluated.

  1. 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.

  2. Molecular dynamics simulation of anionic clays containing glutamic acid

    NASA Astrophysics Data System (ADS)

    Xu, Qian; Ni, Zheming; Yao, Ping; Li, Yuan

    2010-08-01

    Supra-molecular structure of glutamic acid intercalated ZnAl layered double hydroxides (Glu-ZnAl-LDH) was modeled by molecular dynamics (MD) methods. Hydrogen bonding, hydration and swelling properties of Glu-LDH have been investigated. For Nw < 8, interlayer spacing dc increased slowly. For Nw ⩾ 8, the variation of dc followed the linear equation dc = 0.432 Nw + 8.837 ( R2 = 0.9983). The hydration energy gradually increased as water content increased until Nw = 36. Glu-LDH exhibited a tendency to adsorb water continuously at high water content. Hydration of Glu-LDH occurred as follows: Water molecules initially formed hydrogen bond with layers and anions. When A-W type H-bonds gradually reached a saturation state, water molecules continued to form hydrogen bonds with the hydroxyls of the layers. The L-W type H-bonds gradually substituted the L-A type H-bonds and Glu anions moved to the center of an interlayer and then separated with the layers. Last, a well-ordered structural water layer was formed on the surface hydroxyls of Glu-LDH. The lower releasing content of Glu-LDH maybe was influenced by the lower balance hydration energy and existence of L-A type H-bonds in high water content.

  3. 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.

  4. 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.

  5. Anions in Nucleic Acid Crystallography.

    PubMed

    D'Ascenzo, Luigi; Auffinger, Pascal

    2016-01-01

    Nucleic acid crystallization buffers contain a large variety of chemicals fitting specific needs. Among them, anions are often solely considered for pH-regulating purposes and as cationic co-salts while their ability to directly bind to nucleic acid structures is rarely taken into account. Here we review current knowledge related to the use of anions in crystallization buffers along with data on their biological prevalence. Chloride ions are frequently identified in crystal structures but display low cytosolic concentrations. Hence, they are thought to be distant from nucleic acid structures in the cell. Sulfate ions are also frequently identified in crystal structures but their localization in the cell remains elusive. Nevertheless, the characterization of the binding properties of these ions is essential for better interpreting the solvent structure in crystals and consequently, avoiding mislabeling of electron densities. Furthermore, understanding the binding properties of these anions should help to get clues related to their potential effects in crowded cellular environments.

  6. Incorporating interfacial phenomena in solidification models

    NASA Technical Reports Server (NTRS)

    Beckermann, Christoph; Wang, Chao Yang

    1994-01-01

    A general methodology is available for the incorporation of microscopic interfacial phenomena in macroscopic solidification models that include diffusion and convection. The method is derived from a formal averaging procedure and a multiphase approach, and relies on the presence of interfacial integrals in the macroscopic transport equations. In a wider engineering context, these techniques are not new, but their application in the analysis and modeling of solidification processes has largely been overlooked. This article describes the techniques and demonstrates their utility in two examples in which microscopic interfacial phenomena are of great importance.

  7. Incorporating interfacial phenomena in solidification models

    NASA Technical Reports Server (NTRS)

    Beckermann, Christoph; Wang, Chao Yang

    1994-01-01

    A general methodology is available for the incorporation of microscopic interfacial phenomena in macroscopic solidification models that include diffusion and convection. The method is derived from a formal averaging procedure and a multiphase approach, and relies on the presence of interfacial integrals in the macroscopic transport equations. In a wider engineering context, these techniques are not new, but their application in the analysis and modeling of solidification processes has largely been overlooked. This article describes the techniques and demonstrates their utility in two examples in which microscopic interfacial phenomena are of great importance.

  8. Interfacial reactions in titanium-matrix composites

    SciTech Connect

    Yang, J.M.; Jeng, S.M. )

    1989-11-01

    A study of the interfacial reaction characteristics of SiC fiber-reinforced titanium aluminide and disordered titanium alloy composites has determined that the matrix alloy compositions affect the microstructure and the distribution of the reaction products, as well as the growth kinetics of the reaction zones. The interfacial reaction products in the ordered titanium aluminide composite are more complicated than those in the disordered titanium-alloy composite. The activation energy of the interfacial reaction in the ordered titanium aluminide composite is also higher than that in the disordered titanium alloy composite. Designing an optimum interface is necessary to enhance the reliability and service life at elevated temperatures. 16 refs.

  9. Exploring the location and orientation of 4-( N, N-dimethylamino) cinnamaldehyde in anionic, cationic and non-ionic micelles

    NASA Astrophysics Data System (ADS)

    Panja, Subhasis; Chowdhury, Papia; Chakravorti, Sankar

    2003-01-01

    This Letter reports probing of non-ionic, anionic and cationic micelles utilizing different dual emission properties of 4-( N, N-dimethylamino) cinnamaldehyde. Twisted intramolecular charge transfer (TICT) band is more enhanced and blue shifted in non-ionic micelle than those are in ionic micelles. In non-ionic micelle, the molecule enters in the core region whereas, in ionic micelles, it is anchored in the interfacial region with different orientations. Micellar-water interface electric field in ionic micelles was found to have profound effect on TICT decay time. Interestingly, inorganic salt-counterion binding helps the acceptor moiety to enter into the core region in anionic micelle.

  10. Structural and electronic analysis of Li/Al layered double hydroxides and their adsorption for CO2

    NASA Astrophysics Data System (ADS)

    Hou, Xin-Juan; Li, Huiquan; He, Peng; Sun, Zhenhua; Li, Shaopeng

    2017-09-01

    The most stable structures and electronic properties of different Li/Al layered double hydroxides models (i.e., Li/Al-X, X = F-, Cl-, Br-, OH-, NO3-, CO32-, SO42-) and their hydrates, the adsorption of CO2 on Li/Al-X (X = Cl-, NO3-, CO32-) were ascertained by means of density functional theory. Results revealed that the planes of NO3- and CO32- are parallel with the layers in dehydrated state, although the plane of NO3- becomes vertical with the layers upon the introduction of water molecules. Electronic density analysis suggested that SO42- and CO32- significantly strengthens the reducibility of the Li/Al layered double hydroxides. The distribution of the frontier orbitals indicated the high reactivity of the anions and hydroxyl groups of the layers. The orders of the predicted stability are F- > Cl- > Br- > NO3- for the monovalent anions and SO42- > CO32- for the divalent anions. The calculated adsorption energies of CO2 in Li/Al-X (X = Cl-, NO3-, CO3-) supported the experimental observation that Li/Al-CO3 exhibits higher CO2 capture capacity than Li/Al-NO3 and Li/Al-Cl. Non-covalent interaction analysis indicated that the interactions among mineral surfaces, anions, water and CO2 are dominated by H-bonds, electrostatic interactions, and van der Waals forces. In addition, radial distribution functions were applied to provide insight for the interaction of water or CO2 with carbonate ion and hydroxyl layers.

  11. Chemisorption of Hydroxide on 2D Materials From DFT Calculations: Graphene Versus Hexagonal Boron Nitride

    PubMed Central

    Grosjean, Benoit; Pean, Clarisse; Siria, Alessandro; Bocquet, Lyderic; Vuilleumier, Rodolphe; Bocquet, Marie-Laure

    2017-01-01

    Recent nanofluidic measurements revealed strongly different surface charge measurements for boron-nitride and graphitic nanotubes when in contact with saline and alkaline water. 1,2 These observations contrast with the similar reactivity of a graphene layer and its boron nitride counterpart, using Density Functional Theory (DFT) framework, for intact and dissociative adsorption of gaseous water molecules. Here, we investigate, by DFT in implicit water, single and multiple adsorption of anionic hydroxide on single layers. A differential adsorption strength is found in vacuum for the first ionic adsorption on the two materials – chemisorbed on BN while physisorbed on graphene. The effect of implicit solvation reduces all adsorption values resulting in a favorable (non-favorable) adsorption on BN (graphene). We also calculate a pKa ≃ 6 for BN in water, in good agreement with experiments. Comparatively, the unfavorable results for graphene in water echoes the weaker surface charge measurements, but points to an alternative scenario. PMID:27809540

  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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    The synthesis of Mg2Al-NO3 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.

  14. 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.

  15. Intercalation of luminescent Europium(III) complexes in layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Sarakha, L.; Forano, C.; Boutinaud, P.

    2009-01-01

    Anionic Europium(III) complexes EuL1, EuL2 and EuL3 (L1 = tris (dipicolinate), L2 = diethylenetriaminepentaacetate, L3 = disulfonated bathophenanthroline tris(dibenzoylmethanate) were intercalated in Zn 2Al(OH) 6Cl, nH 2O and Zn 4Al(OH) 10Cl, nH 2O layered double hydroxides (LDHs). Intercalation was confirmed by X-ray diffraction, vibration spectroscopy and photoluminescence measurements, using Eu(III) as a local structural probe. Information on host-guest interactions in the hybrid materials were deduced by analyzing the intensity parameter Ω 2, the energy position of the 5D 0- 7F 0 transition and the emission decay profile of the prominent hypersensitive red 5D 0- 7F 2 emission.

  16. EFFECT OF HYDROCARBON PHASE ON INTERFACIAL AND THERMODYNAMIC PROPERTIES OF TWO ANIONIC GLYCOLIPID BIOSURFACTANTS. (R827132)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Spontaneous magnetization in Ni-Al and Ni-Fe layered double hydroxides.

    PubMed

    Coronado, Eugenio; Galán-Mascarós, José R; Martí-Gastaldo, Carlos; Ribera, Antonio; Palacios, Elías; Castro, Miguel; Burriel, Ramón

    2008-10-06

    Layered double hydroxides containing paramagnetic Ni (II) and diamagnetic/paramagnetic Al (III)/Fe (III) ions have been prepared and characterized. Ni 2Al(OH) 6(NO 3). nH 2O ( 1), Ni 2Fe(OH) 6(NO 3). nH 2O ( 2), Ni 2Fe(OH) 6(C 6H 8O 4) 0.5. nH 2O ( 3), and Ni 2Fe(OH) 6(C 10H 16O 4) 0.5. nH 2O ( 4) were prepared by coprecipitation at controlled pH as polycrystalline materials with the typical brucite-like structure, with alternating layers of hydroxide and the corresponding anions, which determine the interlayer separation. Magnetic studies show the appearance of spontaneous magnetization between 2 and 15 K for these compounds. Interestingly, the onset temperature for spontaneous magnetization follows a direct relationship with interlayer separation, since this is the only magnetic difference between compounds 2, 3, and 4. Magnetic and calorimetric data indicate that long-range magnetic ordering is not occurring in any of these materials, but rather a freezing of the magnetic system in 3D due to the magnetic disorder and competing intra- and interlayer interactions. Thus, these hydrotalcite-like magnetic materials can be regarded as spin glasses.

  4. 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.

  5. The intercalation of bicyclic and tricyclic carboxylates into layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Khan, Aamir I.; Williams, Gareth R.; Hu, Gang; Rees, Nicholas H.; O'Hare, Dermot

    2010-12-01

    Twenty-four nanocomposites built from layered double hydroxides and bicyclic and tricyclic carboxylates have been synthesised for the first time. Eight carboxylates were successfully intercalated into [LiAl 2(OH) 6]Cl· yH 2O, [Ca 2Al(OH) 6]NO 3· yH 2O, and [Mg 2Al(OH) 6]NO 3· yH 2O, and the products fully characterised. Guest species incorporated include 1-adamantane carboxylate (1- AC) and 5-norbornene-2- endo-3- exo-dicarboxylate. In some cases, carbonate anions were co-intercalated with the organic guest, and in others poorly crystalline aluminium hydroxides formed as by-products. Sharper resonances were observed in the 13C solid-state NMR spectra of the 1- AC intercalates than in the spectrum of pure 1- AC, suggesting increased order in the arrangement of the cyclic cages in the intercalates. Where possible, time-resolved in situ X-ray diffraction was employed to study the nanoscopic steps involved in the intercalation reactions. These investigations showed that the reactions are one-step processes, proceeding directly to the fully exchanged intercalate with no intermediate phases. The intercalation processes were found to be nucleation controlled.

  6. Aluminium substitution in iron(II III)-layered double hydroxides: Formation and cationic order

    NASA Astrophysics Data System (ADS)

    Ruby, Christian; Abdelmoula, Mustapha; Aissa, Rabha; Medjahdi, Ghouti; Brunelli, Michela; François, Michel

    2008-09-01

    The formation and the modifications of the structural properties of an aluminium-substituted iron(II-III)-layered double hydroxide (LDH) of formula Fe4IIFe(2-6y)IIIAl6yIII (OH) 12 SO 4, 8H 2O are followed by pH titration curves, Mössbauer spectroscopy and high-resolution X-ray powder diffraction using synchrotron radiation. Rietveld refinements allow to build a structural model for hydroxysulphate green rust, GR(SO 42-), i.e. y=0, in which a bilayer of sulphate anions points to the Fe 3+ species. A cationic order is proposed to occur in both GR(SO 42-) and aluminium-substituted hydroxysulphate green rust when y<0.08. Variation of the cell parameters and a sharp decrease in average crystal size and anisotropy are detected for an aluminium content as low as y=0.01. The formation of Al-GR(SO 42-) is preceded by the successive precipitation of Fe III and Al III (oxy)hydroxides. Adsorption of more soluble Al III species onto the initially formed ferric oxyhydroxide may be responsible for this slowdown of crystal growth. Therefore, the insertion of low aluminium amount ( y˜0.01) could be an interesting way for increasing the surface reactivity of iron(II-III) LDH that maintains constant the quantity of the reactive Fe II species of the material.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Recovery of small bioparticles by interfacial partitioning.

    PubMed

    Jauregi, P; Hoeben, M A; van der Lans, R G J M; Kwant, G; van der Wielen, L A M

    2002-05-20

    In this article, a qualitative study of the recovery of small bioparticles by interfacial partitioning in liquid-liquid biphasic systems is presented. A range of crystallised biomolecules with varying polarities have been chosen such as glycine, phenylglycine and ampicillin. Liquid-liquid biphasic systems in a range of polarity differences were selected such as an aqueous two-phase system (ATPS), water-butanol and water-hexanol. The results indicate that interfacial partitioning of crystals occurs even when their density exceeds that of the individual liquid phases. Yet, not all crystals partition to the same extent to the interface to form a stable and thick interphase layer. This indicates some degree of selectivity. From the analysis of these results in relation to the physicochemical properties of the crystals and the liquid phases, a hypothetical mechanism for the interfacial partitioning is deduced. Overall these results support the potential of interfacial partitioning as a large scale separation technology.

  12. 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.

  13. Using the pseudophase kinetic model to interpret chemical reactivity in ionic emulsions: determining antioxidant partition constants and interfacial rate constants.

    PubMed

    Gu, Qing; Bravo-Díaz, Carlos; Romsted, Laurence S

    2013-06-15

    Kinetic results obtained in cationic and anionic emulsions show for the first time that pseudophase kinetic models give reasonable estimates of the partition constants of reactants, here t-butylhydroquinone (TBHQ) between the oil and interfacial region, P(O)(I), and the water and interfacial region, P(W)(I), and of the interfacial rate constant, k(I), for the reaction with an arenediazonium ion in emulsions containing a 1:1 volume ratio of a medium chain length triglyceride, MCT, and aqueous acid or buffer. The results provide: (a) an explanation for the large difference in pH, >4 pH units, required to run the reaction in CTAB (pH 1.54, added HBr) and SDS (pH 5.71, acetate buffer) emulsions; (b) reasonable estimates of PO(I) and k(I) in the CTAB emulsions; (c) a sensible interpretation of added counterion effects based on ion exchange in SDS emulsions (Na(+)/H3O(+) ion exchange in the interfacial region) and Donnan equilibrium in CTAB emulsions (Br(-) increasing the interfacial H3O(+)); and (d) the significance of the effect of the much greater solubility of TBHQ in MCT versus octane, 1000/1, as the oil. These results should aid in interpreting the effects of ionic surfactants on chemical reactivity in emulsions in general and in selecting the most efficient antioxidant for particular food applications.

  14. An Experiment in Mixing and Interfacial Stress.

    DTIC Science & Technology

    1985-02-01

    bottom stress above indicated is disappointing. The cause of the disagree- ment in one part is the difficulty of low flow measurements and in another...TEST CHART NATIONA fHURIAAll MtDAPPA 𔃻 MISCELLANEOUS PAPER HL-85-1 Fi & Lz ’ IAN EXPERIMENT IN MIXINGIAND USAm op INTERFACIAL STRESS by Garbis H...INTERFACIAL STRESS S. PERFORMING ORG. REPORT NUMBER 7. AUTHOR(e) I. CONTRACT OR GRANT NUMBER) Garbis H. Keulegan 9. PERFORMING ORGANIZATION NAME AND

  15. 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.

  16. Interfacial Instabilities on a Droplet

    NASA Astrophysics Data System (ADS)

    Jalaal, Maziyar; Mehravaran, Kian

    2013-11-01

    The fragmentation of droplets is an essential stage of several natural and industrial applications such as fuel atomization and rain phenomena. In spite of its relatively long history, the mechanism of fragmentation is not clear yet. This is mainly due to small length and time scales as well as the non-linearity of the process. In the present study, two and three-dimensional numerical simulations have been performed to understand the early stages of the fragmentation of an initially spherical droplet. Simulations are performed for high Reynolds and a range of relatively high Weber numbers (shear breakup). To resolve the small-scale instabilities generated over the droplet, a second-order adaptive finite volume/volume of fluids (FV/VOF) method is employed, where the grid resolution is increased with the curvature of the gas-liquid interface as well as the vorticity magnitude. The study is focused on the onset and growth of interfacial instabilities. The role of Kelvin-Helmholtz instability (in surface wave formation) and Rayleigh-Taylor instability (in azimuthal transverse modulation) are shown and the obtained results are compared with the linear instability theories for zero and non-zero vorticity layers. Moreover, the analogy between the fragmentation of a single drop and a co-axial liquid jet is discussed. The current results can be used for the further development of the current secondary atomization models.

  17. 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.

  18. 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.

  19. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 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 (Cr2O3·XH2O...

  20. 21 CFR 73.2326 - Chromium hydroxide green.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 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 the... in coloring externally applied cosmetics, including those intended for use in the area of the eye, in...

  1. 21 CFR 73.2326 - Chromium hydroxide green.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 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 the... in coloring externally applied cosmetics, including those intended for use in the area of the eye, in...

  2. 21 CFR 73.1326 - Chromium hydroxide green.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 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 (Cr2O3·XH2O...

  3. 21 CFR 872.3250 - Calcium hydroxide cavity liner.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... (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 a prepared cavity before insertion of restorative material, such as amalgam, to protect the pulp of a tooth...

  4. Anionic and cationic Hofmeister effects on hydrophobic and hydrophilic surfaces.

    PubMed

    Schwierz, Nadine; Horinek, Dominik; Netz, Roland R

    2013-02-26

    Using a two-step modeling approach, we address the full spectrum of direct, reversed, and altered ionic sequences as the charge of the ion, the charge of the surface, and the surface polarity are varied. From solvent-explicit molecular dynamics simulations, we extract single-ion surface interaction potentials for halide and alkali ions at hydrophilic and hydrophobic surfaces. These are used within Poisson-Boltzmann theory to calculate ion density and electrostatic potential distributions at mixed polar/unpolar surfaces for varying surface charge. The resulting interfacial tension increments agree quantitatively with experimental data and capture the Hofmeister series, especially the anomaly of lithium, which is difficult to obtain using continuum theory. Phase diagrams that feature different Hofmeister series as a function of surface charge, salt concentration, and surface polarity are constructed from the long-range force between two surfaces interacting across electrolyte solutions. Large anions such as iodide have a high hydrophobic surface affinity and increase the effective charge magnitude on negatively charged unpolar surfaces. Large cations such as cesium also have a large hydrophobic surface affinity and thereby compensate an external negative charge surface charge most efficiently, which explains the well-known asymmetry between cations and anions. On the hydrophilic surface, the size-dependence of the ion surface affinity is reversed, explaining the Hofmeister series reversal when comparing hydrophobic with hydrophilic surfaces.

  5. 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.

  6. Kinetics of intercalation of fluorescent probes in magnesium-aluminium layered double hydroxide within a multiscale reaction-diffusion framework

    NASA Astrophysics Data System (ADS)

    Saliba, Daniel; Al-Ghoul, Mazen

    2016-11-01

    We report the synthesis of magnesium-aluminium layered double hydroxide (LDH) using a reaction-diffusion framework (RDF) that exploits the multiscale coupling of molecular diffusion with chemical reactions, nucleation and growth of crystals. In an RDF, the hydroxide anions are allowed to diffuse into an organic gel matrix containing the salt mixture needed for the precipitation of the LDH. The chemical structure and composition of the synthesized magnesium-aluminium LDHs are determined using powder X-ray diffraction (PXRD), thermo-gravimetric analysis, differential scanning calorimetry, solid-state nuclear magnetic resonance (SSNMR), Fourier transform infrared and energy dispersive X-ray spectroscopy. This novel technique also allows the investigation of the mechanism of intercalation of some fluorescent probes, such as the neutral three-dimensional rhodamine B (RhB) and the negatively charged two-dimensional 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS), using in situ steady-state fluorescence spectroscopy. The incorporation of these organic dyes inside the interlayer region of the LDH is confirmed via fluorescence microscopy, solid-state lifetime, SSNMR and PXRD. The activation energies of intercalation of the corresponding molecules (RhB and HPTS) are computed and exhibit dependence on the geometry of the involved probe (two or three dimensions), the charge of the fluorescent molecule (anionic, cationic or neutral) and the cationic ratio of the corresponding LDH. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

  7. Nanostructured ZnS and CdS films synthesized using layered double hydroxide films as precursor and template.

    PubMed

    Schwenzer, Birgit; Pop, Lia Z; Neilson, James R; Sbardellati, Timothy B; Morse, Daniel E

    2009-02-16

    Anion exchange reactions in layered double hydroxide films (M(OH)(2-x)(NO(3))(x).mH(2)O) followed by solid state conversion reactions are shown to yield micrometer-sized unsupported metal sulfide (M = Zn, Cd) films with unique textured morphologies. The characteristic three-dimensional nanostructured film morphology and crystallinity of the initial films are retained in the metal sulfide films although these conversion reactions involve anion exchanges concomitant with significant rearrangements of the crystal structures. Surface areas of 42 m(2)/g for zinc sulfide and 50 m(2)/g for cadmium sulfide thin films are observed. These values correspond to an increase in surface area of 75% for the Zn(5)(OH)(8)(NO(3))(2).2H(2)O to zinc sulfide conversion, while the cadmium sulfide films exhibit more than three times the surface area of their precursor material, Cd(OH)(NO(3)).H(2)O. The three-dimensional morphology of the resulting films is thus observed to combine the physical properties of the bulk materials with the advantages of higher surface areas typically associated with nanostructured or porous materials. The layered double hydroxide materials used in this study to provide both structural and chemical templates were prepared using the mild conditions of a biologically inspired vapor-diffusion catalytic synthesis.

  8. Air-water interfacial areas in unsaturated soils: Evaluation of interfacial domains

    NASA Astrophysics Data System (ADS)

    Costanza-Robinson, Molly S.; Brusseau, Mark L.

    2002-10-01

    A gas-phase miscible-displacement method, using decane as an interfacial tracer, was used to measure air-water interfacial areas for a sand with water contents ranging from ˜2% to 20%. The expected trend of decreasing interfacial areas with increasing water contents was observed. The maximum estimated interfacial area of 19,500 cm-1 appears reasonable given it is smaller than the measured surface area of the porous medium (60,888 cm-1). Comparison of the experimental data presented herein with literature data provided further insight into the characterization of the air-water interface in unsaturated porous media. Specifically, comparison of interfacial areas measured using gas-phase versus aqueous-phase methods indicates that the gas-phase method generally yields larger interfacial areas than the aqueous-phase methods, even when accounting for differences in water content and physical properties of the porous media. The observations are consistent with proposed differences in interfacial accessibility of the aqueous- and gas-phase tracers. Evaluation of the data in light of functional interfacial domains, described herein, yields the hypothesis that aqueous interfacial tracers measure primarily air-water interfaces formed by "capillary water," while gas-phase tracers measure air-water interfaces formed by both capillary and surface-adsorbed (film) water. The gas- and aqueous-phase methods may each provide interfacial area information that is more relevant to specific problems of interest. For example, gas-phase interfacial area measurements may be most relevant to contaminant transport in unsaturated systems, where retention at the air-water interface may be significant. Conversely, the aqueous-phase methods may yield information with direct bearing on multiphase flow processes that are dominated by capillary-phase behavior.

  9. 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.

  10. 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.

  11. 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.

  12. Binding Hydrated Anions with Hydrophobic Pockets.

    PubMed

    Sokkalingam, Punidha; Shraberg, Joshua; Rick, Steven W; Gibb, Bruce C

    2016-01-13

    Using a combination of isothermal titration calorimetry and quantum and molecular dynamics calculations, we demonstrate that relatively soft anions have an affinity for hydrophobic concavity. The results are consistent with the anions remaining partially hydrated upon binding, and suggest a novel strategy for anion recognition.

  13. Interfacial phase-change memory.

    PubMed

    Simpson, R E; Fons, P; Kolobov, A V; Fukaya, T; Krbal, M; Yagi, T; Tominaga, J

    2011-07-03

    Phase-change memory technology relies on the electrical and optical properties of certain materials changing substantially when the atomic structure of the material is altered by heating or some other excitation process. For example, switching the composite Ge(2)Sb(2)Te(5) (GST) alloy from its covalently bonded amorphous phase to its resonantly bonded metastable cubic crystalline phase decreases the resistivity by three orders of magnitude, and also increases reflectivity across the visible spectrum. Moreover, phase-change memory based on GST is scalable, and is therefore a candidate to replace Flash memory for non-volatile data storage applications. The energy needed to switch between the two phases depends on the intrinsic properties of the phase-change material and the device architecture; this energy is usually supplied by laser or electrical pulses. The switching energy for GST can be reduced by limiting the movement of the atoms to a single dimension, thus substantially reducing the entropic losses associated with the phase-change process. In particular, aligning the c-axis of a hexagonal Sb(2)Te(3) layer and the 〈111〉 direction of a cubic GeTe layer in a superlattice structure creates a material in which Ge atoms can switch between octahedral sites and lower-coordination sites at the interface of the superlattice layers. Here we demonstrate GeTe/Sb(2)Te(3) interfacial phase-change memory (IPCM) data storage devices with reduced switching energies, improved write-erase cycle lifetimes and faster switching speeds.

  14. 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.

  15. 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.

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

    SciTech Connect

    Kruzic, Jamie Joseph

    2001-01-01

    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.

  17. Novel HCN sorbents based on layered double hydroxides: sorption mechanism and performance.

    PubMed

    Zhao, Qian; Tian, Senlin; Yan, Linxia; Zhang, Qiulin; Ning, Ping

    2015-03-21

    Layered double hydroxides (LDHs) and layered double oxides (LDOs) have been prepared and used as sorbents for hydrogen cyanide (HCN). Based on results from sorbent optimization experiments, the optimal performance for HCN removal was found in Ni-Al LDH. As evidenced by fixed-bed sorption studies, the Ni-Al LDO with the greatest surface area showed better performance and outperformed products calcined at 200, 400, or 500 °C, whereas, the Ni-Al LDH showed a more twofold higher sorption capacity than the Ni-Al LDO. Investigation of the mechanisms between HCN and sorbents reveals that the HCN removal by the Ni-Al LDH and Ni-Al LDO leads to the formation of the complex anion, [Ni(CN)4](2-). Nevertheless, the [Ni(CN)4](2-) can enter interlayer region of the Ni-Al LDH due to its anion exchangeability, which endows this LDH with more binding sites, not only on its external surfaces, but also on its internal surfaces located in the interlayer region. In contrast, [Ni(CN)4](2-) were only adsorbed on the external surface of the Ni-Al LDO. As a result, the sorption capacity of the Ni-Al LDH for HCN is twice as high as that of the Ni-Al LDO, which is at 21.55 mg/g.

  18. Dependence of bonding interactions in Layered Double Hydroxides on metal cation chemistry

    NASA Astrophysics Data System (ADS)

    Shamim, Mostofa; Dana, Kausik

    2016-12-01

    The evolution of various Infrared bands of Layered Double Hydroxides (LDH) with variable Zn:Al ratio was analyzed to correlate it with the changes in octahedral metal cation chemistry, interlayer carbonate anion and hydroxyl content of LDH. The synthesized phase-pure LDHs were crystallized as hexagonal 2H polytype with a Manasseite structure. The broad and asymmetric hydroxyl stretching region (2400-4000 cm-1) can be deconvoluted into four different bands. With increase in Zn2+:Al3+ metal ratio, the peak position of stretching frequencies of Al3+sbnd OH and carbonate-bridged hydroxyl (water) decrease almost linearly. Individual band's peak position and area under the curve have been successfully correlated with the carbonate and hydroxyl content of LDH. Due to lowering of symmetry of the carbonate anion, the IR-inactive peak νCsbnd O, symm at 1064 cm-1 becomes IR active. The peak position of metal-oxygen bands and carbonate bending modes are practically unaffected by the Zn2+:Al3+ ratio but the area under the individual M-O bands shows a direct correlation.

  19. 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.

  20. A study of the catalysis of cobalt hydroxide towards the oxygen reduction in alkaline media

    NASA Astrophysics Data System (ADS)

    Wang, Yi; Zhang, Dun; Liu, Huaiqun

    A cobalt hydroxide modified glassy carbon (Co(OH) 2/GC) electrode has been fabricated by a galvanostatic electrodeposition method. The catalytic activity for the oxygen (O 2) reduction reaction (ORR) of this electrode in alkaline media is studied by cyclic voltammetry, rotating disk electrode voltammetry, and rotating ring-disk electrode voltammetry. The O 2 reduction at the Co(OH) 2/GC disk electrode has been found to undergo an electrochemical process followed by sequential disproportionation of the electrochemical reduction intermediates, i.e., superoxide anion (O 2 rad -) and hydrogen peroxide anion (HO 2 -) in 0.1 M KOH solution. The Co(OH) 2 is first found to possess an excellent catalytic activity not only for the disproportionation of the O 2 rad - produced into O 2 and HO 2 - but also for that of the HO 2 - produced, combined with electrochemical reduction of O 2 mediated by surface functional groups at the carbon electrode surface. The Co(OH) 2 is a potential electrode material for the ORR in alkaline fuel cells and metal-air batteries.

  1. 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.

  2. Universal biomimetic preparation and immobilization of layered double hydroxide films and adsorption behavior

    NASA Astrophysics Data System (ADS)

    Zhou, Wei; Zhang, Wenpeng; Chen, Zilin

    2017-01-01

    Preparation and immobilization of layered double hydroxides (LDHs) film onto multiple substrates is important and challenging in functional materials fields by date. In this work, a simple and universal polydopamine (PD)-based layer-by-layer assembly strategy was developed for the immobilization of LDHs film onto surfaces such as polypropylene chip, glass slides and metal coins. The surface of substrates was firstly modified by polydopamine functionalization, and then LDHs film was synthesized via urea method and directly immobilized on the PD layer by in situ growing strategy in one step. The PD layer as well as the final LDHs film was characterized by energy dispersive X-ray spectroscopy, scanning electron microscope, infrared spectroscopy, X-ray diffraction pattern and X-ray photoelectron spectra. It has been demonstrated the formation of the dense and homogeneous nanoscaled LDHs film with 400 nm thickness. Adsorption behavior of the fabricated NiAl-LDHs film toward anionic dyes and pharmaceuticals was further assessed. To demonstrate their extensive application, fast and high efficient adsorption of anionic dyes and pharmaceuticals was achieved by NiAl-LDHs-modified polypropylene centrifugal tube.

  3. 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.

  4. Synthesis and characterization of 10-hydroxycamptothecin - sebacate - layered double hydroxide nanocomposites

    NASA Astrophysics Data System (ADS)

    Pang, Xiujiang; Ma, Xiuming; Li, Dongxiang; Hou, Wanguo

    2013-02-01

    10-Hydroxycamptothecin (HCPT) as a hydrophobic anticancer drug brings many challenges in the clinical applications due to its poor water solubility and the presence of a chemically unstable lactone ring. In this work, the nanocomposites of HCPT intercalated layered double hydroxide (LDH) were prepared by a secondary intercalation method, and the encapsulated HCPT could keep the biologically active lactone form. A Zn-Al-NO3 LDH was pillared with sebacate anions by a co-precipitation method in an aqueous medium, and then HCPT was intercalated into the LDH's gallery via hydrophobic interaction in an ethanol medium. The parallel alkyl chains of perpendicularly arranged sebacate anions in the LDH gallery provide a hydrophobic space for the drug intercalation. The in vitro release kinetics of HCPT from the nanocomposites could be fitted with the pseudo-second-order kinetic model, and the diffusion of HCPT through the LDH particles played an important role in controlling the drug release. The nanocomposites can be considered as a potential drug delivery system.

  5. Surface-charging behavior of Zn-Cr layered double hydroxide.

    PubMed

    Rojas Delgado, R; Arandigoyen Vidaurre, M; De Pauli, C P; Ulibarri, M A; Avena, M J

    2004-12-15

    A Zn-Cr layered double hydroxide (LDH) having the formula Zn(2)Cr(OH)(6)Cl(0.7)(CO(3))(0.15)2.1H(2)O was synthesized and characterized by powder X-ray diffraction, infrared spectroscopy, acid-base potentiometric titration, mass titration, electrophoretic mobility, and modeling of the electrical double layer. Adsorption of alizarin was also performed in order to show some particular features of the HDL. Net hydroxyl adsorption, which increases with increasing pH and decreasing supporting electrolyte concentration, takes place above pH 5. The electrophoretic mobility of the particles was always positive and it decreased when the pH was higher than 9. An isoelectric point of 12 could be estimated by extrapolating the data. The modified MUSIC model was used to estimate deprotonation constants of surface groups and different adsorption models were compared. Good fit of hydroxyl adsorption and electrophoresis could be achieved by considering both OH(-)/Cl(-) exchange at structural sites and proton desorption from surface hydroxyl groups. The modeling, in agreement with alizarin adsorption, indicates that most of the structural positive charge of the LDH is screened at the surface by exchanged anions and negatively charged surface groups. It also suggests that only structural charge sites initially neutralized by chloride ions are active for anion exchange. The remaining sites are blocked by carbonate and do not participate in the exchange.

  6. Measuring air-water interfacial areas with X-ray microtomography and interfacial partitioning tracer tests.

    PubMed

    Brusseau, Mark L; Peng, Sheng; Schnaar, Gregory; Murao, Asami

    2007-03-15

    Air-water interfacial areas as a function of water saturation were measured for a sandy, natural porous medium using two methods, aqueous-phase interfacial partitioning tracer tests and synchrotron X-ray microtomography. In addition, interfacial areas measured in a prior study with the gas-phase interfacial partitioning tracer-test method for the same porous medium were included for comparison. For all three methods, total air-water interfacial areas increased with decreasing water saturation. The interfacial areas measured with the tracer-test methods were generally larger than those obtained from microtomography, and the disparity increased as water saturation decreased. The interfacial areas measured by microtomography extrapolated to a value (147 cm(-1)) very similar to the specific solid surface area (151 cm(-1)) calculated using the smooth-sphere assumption, indicating that the method does not characterize the area associated with microscopic surface heterogeneity (surface roughness, microporosity). This is consistent with the method resolution of approximately 12 microm. In contrast, the interfacial areas measured with the gas-phase tracer tests approached the N2/BET measured specific solid surface area (56000 cm(-1)), indicating that this method does characterize the interfacial area associated with microscopic surface heterogeneity. The largest interfacial area measured with the aqueous-phase tracer tests was 224 cm(-1), while the extrapolated maximum interfacial area was approximately 1100 cm(-1). Both of these values are larger than the smooth-sphere specific solid surface area but much smaller than the N2/BET specific solid surface area, which suggests that the method measures a limited portion of the interfacial area associated with microscopic surface heterogeneity. All three methods provide measures of total (capillary + film) interfacial area, a primary difference being that the film-associated area is a smooth-surface equivalent for the

  7. Modeling anion adsorption on kaolinite

    SciTech Connect

    Weerasooriya, R.; Wickramarathna, H.U.S.

    1999-05-15

    Anion adsorption onto kaolinite was quantified using the triple layer surface complexation model. Fluoride adsorption data were described by both anion exchange and H-bonded complexation mechanisms. The outer-sphere complexation mechanism was used to describe the weak adsorption of Cl{sup {minus}}, Br{sup {minus}}, and I{sup {minus}} on kaolinite. The F{sup {minus}} adsorption in the presence of Br{sup {minus}} or I{sup {minus}} was decreased over a range of pH 4--5 whereas Cl{sup {minus}} showed a negligible effect. Competition for binding sites appeared to be an important factor in determining the adsorptive behavior of F{sup {minus}} in Br{sup {minus}} or I{sup {minus}} mediated systems.

  8. 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.

  9. 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.

  10. Laser cooling of molecular anions.

    PubMed

    Yzombard, Pauline; Hamamda, Mehdi; Gerber, Sebastian; Doser, Michael; Comparat, Daniel

    2015-05-29

    We propose a scheme for laser cooling of negatively charged molecules. We briefly summarize the requirements for such laser cooling and we identify a number of potential candidates. A detailed computation study with C_{2}^{-}, the most studied molecular anion, is carried out. Simulations of 3D laser cooling in a gas phase show that this molecule could be cooled down to below 1 mK in only a few tens of milliseconds, using standard lasers. Sisyphus cooling, where no photodetachment process is present, as well as Doppler laser cooling of trapped C_{2}^{-}, are also simulated. This cooling scheme has an impact on the study of cold molecules, molecular anions, charged particle sources, and antimatter physics.

  11. 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.

  12. In situ analysis of the interfacial reactions between MCMB electrode and organic electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Morigaki, Ken-ichi

    The interfacial phenomena between graphite (mesocarbon-microbeads (MCMB)) electrode and organic electrolyte solution were analyzed by in situ atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopy. The influence of lithium salts (anion species), LiPF 6, LiBF 4, and LiClO 4, on the interfacial reaction, including lithium intercalation into graphite, was investigated in EC+DMC solutions. In situ AFM observation disclosed that morphological changes are quite different from one another depending on the kind of lithium salt (anion). A large expansion of MCMB particle was observed particularly in LiPF 6/EC+DMC. An expansion of MCMB particle started above 1.0 V versus Li/Li + and this expansion seemed to be caused by the decomposition of ternary graphite intercalation compound (GIC) ( C nLi(sol) y), because the expansion remained after de-intercalation of lithium. IRAS spectra of each electrolyte solution showed different behaviors and different reduction products of solvents. double modulation FTIR (DMFTIR) spectra on graphite electrode, which emphasize the surface species, indicated relatively small changes after cathodic polarization. Therefore, the observed morphological changes were caused mainly by the expansion of graphene layers and not by the precipitation of reduction products.

  13. 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.

  14. 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.

  15. Ionol (BHT) produces superoxide anion.

    PubMed

    Smirnova, E G; Lyubimov, Yu I; Malinina, T G; Lyubimova, E Yu; Alexandrushkina, N I; Vanyushin, B F; Kolesova, G M; Yaguzhinsky, L S

    2002-11-01

    In aqueous medium etiolated wheat seedlings release superoxide anion (O2*-). Interaction of a synthetic antioxidant, butylated hydroxytoluene (BHT, ionol), with oxygen in the aqueous medium is accompanied by O2*- formation. This suggests that under certain conditions BHT behaves as a prooxidant. A natural antioxidant, superoxide dismutase (SOD), and also a wound healing preparation, emulsified denatured placenta (EDP), do not exhibit the prooxidant properties. In contrast to BHT, they reduce O2*- production by the etiolated wheat seedling system.

  16. 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

  17. Synthesis, characterisation and anion exchange properties of copper, magnesium, zinc and nickel hydroxy nitrates

    SciTech Connect

    Biswick, Timothy; Jones, William . E-mail: wj10@cam.ac.uk; Pacula, Aleksandra; Serwicka, Ewa

    2006-01-15

    Anion exchange reactions of four structurally related hydroxy salts, Cu{sub 2}(OH){sub 3}NO{sub 3}, Mg{sub 2}(OH){sub 3}NO{sub 3}, Ni{sub 2}(OH){sub 3}NO{sub 3} and Zn{sub 3}(OH){sub 4}(NO{sub 3}){sub 2} are compared and trends rationalised in terms of the strength of the covalent bond between the nitrate group and the matrix cation. Powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA) and elemental analysis are used to characterise the materials. Replacement of the nitrate anions in the zinc and copper salts with benzoate anions is possible although exchange of the zinc salt is accompanied by modification of the layer structure from one where zinc is exclusively six-fold coordinated to a structure where there is both six- and four-fold zinc coordination. Magnesium and nickel hydroxy nitrates, on the other hand, hydrolyse to their respective metal hydroxides. -- Graphical abstract: PXRD patterns of exchange products of (a) Zn{sub 3}(OH){sub 4}(NO{sub 3}){sub 2} (b) Zn{sub 5}(OH){sub 8}(NO{sub 3}){sub 2}.2H{sub 2}O and (c) Cu{sub 2}(OH){sub 3}NO{sub 3} with benzoate anions.

  18. Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

    NASA Astrophysics Data System (ADS)

    Rambo, Brett M.; Silver, Eric S.; Bielawski, Christopher W.; Sessler, Jonathan L.

    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 noncovalent interactions (e.g., hydrogen bonding and electrostatic interactions) provides a route to not only sensitive but also selective polymeric materials. Furthermore, these systems have been utilized in the development of polymers capable of extracting anionic species from aqueous media. These latter materials may lead to advances in water purification and treatment of diseases resulting from surplus ions.

  19. Hosting anions. The energetic perspective.

    PubMed

    Schmidtchen, Franz P

    2010-10-01

    Hosting anions addresses the widely spread molecular recognition event of negatively charged species by dedicated organic compounds in condensed phases at equilibrium. The experimentally accessible energetic features comprise the entire system including the solvent, any buffers, background electrolytes or other components introduced for e.g. analysis. The deconvolution of all these interaction types and their dependence on subtle structural variation is required to arrive at a structure-energy correlation that may serve as a guide in receptor construction. The focus on direct host-guest interactions (lock-and-key complementarity) that have dominated the binding concepts of artificial receptors in the past must be widened in order to account for entropic contributions which constitute very significant fractions of the total free energy of interaction. Including entropy necessarily addresses the ambiguity and fuzziness of the host-guest structural ensemble and requires the appreciation of the fact that most liquid phases possess distinct structures of their own. Apparently, it is the perturbation of the intrinsic solvent structure occurring upon association that rules ion binding in polar media where ions are soluble and abundant. Rather than specifying peculiar structural elements useful in anion binding this critical review attempts an illumination of the concepts and individual energetic contributions resulting in the final observation of specific anion recognition (95 references).

  20. Rice-husk ash paste and concrete: Some aspects of hydration and the microstructure of the interfacial zone between the aggregate and paste

    SciTech Connect

    Zhang, M.H.; Lastra, R.; Malhotra, V.M.

    1996-06-01

    This paper presents an experimental study on the effects of the incorporation of rice-husk ash (RHA) in cement paste and concrete on the hydration and the microstructure of the interfacial zone between the aggregate and paste. The influence on the compressive strength of concrete is discussed, and the results are compared with those obtained with the control portland cement concrete and concrete incorporating silica fume. As for ordinary portland cement paste, it was found that calcium hydroxide and calcium silicate hydrates [C-S-H] were the major hydration and reaction products for the HA paste. Because of the pozzolanic reaction, the paste incorporating RHA had lower Ca(OH){sub 2} content than the control portland cement paste. The incorporation of the RHA in concrete reduced its porosity and the Ca(OH){sub 2} amount in the interfacial zone; the width of the interfacial zone between the aggregate and the cement paste was also reduced compared with the control portland cement composite. However, the porosity in the interfacial zone of the rice-husk ash composite was higher than that of the silica fume composite. The incorporation of the RHA in the cement paste did not increase its compressive strength compared with that of the control. The higher compressive strength of the RHA concrete compared with that of the control is due probably to the reduced porosity, reduced Ca(OH){sub 2}, and reduced width of the interfacial zone between the paste and the aggregate.

  1. Selenium Sequestration in a Cationic Layered Rare Earth Hydroxide: A Combined Batch Experiments and EXAFS Investigation.

    PubMed

    Zhu, Lin; Zhang, Linjuan; Li, Jie; Zhang, Duo; Chen, Lanhua; Sheng, Daopeng; Yang, Shitong; Xiao, Chengliang; Wang, Jianqiang; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2017-08-01

    Selenium is of great concern owing to its acutely toxic characteristic at elevated dosage and the long-term radiotoxicity of (79)Se. The contents of selenium in industrial wastewater, agricultural runoff, and drinking water have to be constrained to a value of 50 μg/L as the maximum concentration limit. We reported here the selenium uptake using a structurally well-defined cationic layered rare earth hydroxide, Y2(OH)5Cl·1.5H2O. The sorption kinetics, isotherms, selectivity, and desorption of selenite and selenate on Y2(OH)5Cl·1.5H2O at pH 7 and 8.5 were systematically investigated using a batch method. The maximum sorption capacities of selenite and selenate are 207 and 124 mg/g, respectively, both representing the new records among those of inorganic sorbents. In the low concentration region, Y2(OH)5Cl·1.5H2O is able to almost completely remove selenium from aqueous solution even in the presence of competitive anions such as NO3(-), Cl(-), CO3(2-), SO4(2-), and HPO4(2-). The resulting concentration of selenium is below 10 μg/L, well meeting the strictest criterion for the drinking water. The selenate on loaded samples could be desorbed by rinsing with concentrated noncomplexing NaCl solutions whereas complexing ligands have to be employed to elute selenite for the material regeneration. After desorption, Y2(OH)5Cl·1.5H2O could be reused to remove selenate and selenite. In addition, the sorption mechanism was unraveled by the combination of EDS, FT-IR, Raman, PXRD, and EXAFS techniques. Specifically, the selenate ions were exchanged with chloride ions in the interlayer space, forming outer-sphere complexes. In comparison, besides anion exchange mechanism, the selenite ions were directly bound to the Y(3+) center in the positively charged layer of [Y2(OH)5(H2O)](+) through strong bidentate binuclear inner-sphere complexation, consistent with the observation of the higher uptake of selenite over selenate. The results presented in this work confirm that the

  2. 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

  3. Interfacial tension of polyelectrolyte complex coacervate phases.

    SciTech Connect

    Qin, Jian; Priftis, Dimitrios; Farina, R; Perry, Sarah L.; Leon, Lorraine F.; Whitmer, Jonathan; Hoffmann, Kyle; Tirrell, Matthew; de Pablo, Juan J.

    2014-06-01

    We consider polyelectrolyte solutions which, under suitable conditions, phase separate into a liquid-like coacervate phase and a coexisting supernatant phase that exhibit an extremely low interfacial tension. Such interfacial tension provides the basis for most coacervate-based applications, but little is known about it, including its dependence on molecular weight, charge density, and salt concentration. By combining a Debye-Huckel treatment for electrostatic interactions with the Cahn-Hilliard theory, we derive explicit expressions for this interfacial tension. In the absence of added salts, we find that the interfacial tension scales as N-3/2(eta/eta(c)-1)(3/2) near the critical point of the demixing transition, and that it scales as eta(1/2) far away from it, where N is the chain length and eta measures the electrostatic interaction strength as a function of temperature, dielectric constant, and charge density of the polyelectrolytes. For the case with added salts, we find that the interfacial tension scales with the salt concentration psi as N-1/4(1-psi/psi(c))(3/2) near the critical salt concentration psi(c). Our predictions are shown to be in quantitative agreement with experiments and provide a means to design new materials based on polyelectrolyte complexation.

  4. Probing Interfacial Emulsion Stability Controls using Electrorheology

    NASA Astrophysics Data System (ADS)

    Wang, Xiuyu; Brandvik, Amy; Alvarado, Vladimir

    2010-11-01

    The stability of water-in-oil emulsions is controlled by interfacial mechanisms that include oil film rheology of approaching drops and the strength of drop interfaces. Film drainage is mainly a function of the continuous phase rheology. Temperature is used to regulate the viscosity of the continuous phase and hence determine its effect on emulsion stability through film drainage, in contrast with interfacial strength. In this study, one crude oil is used to formulate water-in-oil emulsions. Oil-water interfacial tension is measured to gauge other interfacial changes with temperature. The critical field value, used as proxy of emulsion stability, approaches a plateau value for each crude oil- aqueous solution pair, at sufficiently high temperature (50 ^oC), which is interpreted to reflect the intrinsic drop-coating film resistance to coalescence. Interfacial tension does vary significantly with either aqueous phase composition or temperature. From comparison with previous results, we speculate that drop coating film is composed of a fraction of asphaltic compunds.

  5. On the hierarchy of interfacial dislocation structure

    NASA Astrophysics Data System (ADS)

    Balluffi, R. W.; Olson, G. B.

    1985-04-01

    Many different types of dislocations have been defined in dislocation models for grain boundaries and interphase boundaries. It is emphasized that there is no unique dislocation model for a boundary, and that the formal dislocation content depends upon the choice of the lattice correspondence relating the adjoining lattices. However, it is concluded that no problems of real physical significance arise from this lack of uniqueness. “Best≓, or most useful, descriptions often exist, and these are discussed. A hierarchy consisting of four different types of interfacial dislocations may be distinguished, which is useful in describing the dislocation content of interfaces. These entities are termed: (1) primary interfacial dislocations; (2) secondary interfacial dislocations; (3) coherency interfacial dislocations; and (4) translational interfacial dislocations. While there may be a lack of agreement on terminology in the literature, it is believed that these dislocation types are distinguishable and play unique roles in useful dislocation models for interfaces. Detailed descriptions of these dislocation types are given, and actual examples in real interfaces are presented. It is concluded that dislocation descriptions of interface structures become of purely formal significance in the limit of fully incoherent interfaces since the cores are then delocalized. The utility of various dislocation descriptions therefore depends on the degree to which various types of local coherency exist.

  6. Debye-Hückel theory for interfacial geometries.

    PubMed

    Netz, R R

    1999-09-01

    The Debye-Hückel theory for bulk electrolyte solutions is generalized to planar interfacial geometries, including screening effects due to mobile salt ions which are confined to the interface and solutions with in general different salt concentrations and dielectric constants on the two sides of the interface. We calculate the general Debye-Hückel interaction between fixed test charges, and analyze a number of relevant special cases as applicable to charged colloids and charged polymers. Salty interfaces, which are experimentally realized by monolayers or bilayers made of cationic and anionic surfactants or lipids, exert a strong attraction on charged particles of either sign at large separations from the interface; at short distances image-charge repulsion sets in. Likewise, the effective interactions between charged particles are strongly modified in the neighborhood of such a salty interface. On the other hand, charged particles which are immersed in a salt solution are repelled from the air (or a substrate) interface, and the interaction between two charges decays algebraically close to such an interface. These general results have experimentally measurable consequences for the adsorption of charged colloids or charged polymers at monolayers, solid substrates, and interfaces.

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

    PubMed

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

    2010-12-07

    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).

  8. 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.

  9. 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.

  10. Recent Advances in Solid Catalysts Obtained by Metalloporphyrins Immobilization on Layered Anionic Exchangers: A Short Review and Some New Catalytic Results.

    PubMed

    Nakagaki, Shirley; Mantovani, Karen Mary; Machado, Guilherme Sippel; Castro, Kelly Aparecida Dias de Freitas; Wypych, Fernando

    2016-02-29

    Layered materials are a very interesting class of compounds obtained by stacking of two-dimensional layers along the basal axis. A remarkable property of these materials is their capacity to interact with a variety of chemical species, irrespective of their charge (neutral, cationic or anionic). These species can be grafted onto the surface of the layered materials or intercalated between the layers, to expand or contract the interlayer distance. Metalloporphyrins, which are typically soluble oxidation catalysts, are examples of molecules that can interact with layered materials. This work presents a short review of the studies involving metalloporphyrin immobilization on two different anionic exchangers, Layered Double Hydroxides (LDHs) and Layered Hydroxide Salts (LHSs), published over the past year. After immobilization of anionic porphyrins, the resulting solids behave as reusable catalysts for heterogeneous oxidation processes. Although a large number of publications involving metalloporphyrin immobilization on LDHs exist, only a few papers have dealt with LHSs as supports, so metalloporphyrins immobilized on LHSs represent a new and promising research field. This work also describes new results on an anionic manganese porphyrin (MnP) immobilized on Mg/Al-LDH solids with different nominal Mg/Al molar ratios (2:1, 3:1 and 4:1) and intercalated with different anions (CO₃(2-) or NO₃(-)). The influence of the support composition on the MnP immobilization rates and the catalytic performance of the resulting solid in cyclooctene oxidation reactions will be reported.

  11. Facile synthesis of methotrexate intercalated layered double hydroxides: particle control, structure and bioassay explore.

    PubMed

    Tian, De-Ying; Liu, Zhen-Lei; Li, Shu-Ping; Li, Xiao-Dong

    2014-12-01

    To study the influence of particle size on drug efficacy and other properties, a series of methotrexate intercalated layered double hydroxides (MTX/LDHs) were synthesized through the traditional coprecipitation method, using a mixture of water and polyethylene glycol (PEG-400) as the solvent. To adjust the particle size of MTX/LDHs, the dropping way, the volume ratio of water to PEG-400 and different hydrothermal treatment time changed accordingly, and the results indicate that the particle size can be controlled between 90 and 140 nm. Elemental C/H/N and inductive coupled plasma (ICP) analysis indicated that different synthesis conditions almost have no effect on the compositions of the nanohybrids. X-ray diffraction (XRD) patterns manifested the successful intercalation of MTX anions into the LDH interlayers, and it's also found out that different volume ratios of water to PEG-400 and variable dropping way can affect the crystallinity of the final samples, i.e., the volume ratio of 3:1 and pH decreasing are proved to be optimum conditions. Furthermore, both antiparallel monolayer and bilayers adopting different orientations are suggested for four samples from XRD results. Fourier transform infrared spectroscopy (FTIR) investigations proved the coexistence of CO3(2-) and MTX anions in the interlayer of the nanohybrids. MTX/LDH particles exhibited hexagonal platelet morphology with round corner and different dropping ways can affect the morphology greatly. Moreover, a DSC study indicated that longer time treatment can weaken the bond between the MTX anions and LDH layers. The kinetic release profiles told us that larger MTX/LDH particles have enhanced the ability of LDH layers to protect interlayer molecules. At last, the bioassay study indicated that the nanohybrids with larger diameters have higher tumor suppression efficiency.

  12. 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.

  13. Layered double hydroxides as supports for intercalation and sustained release of antihypertensive drugs

    SciTech Connect

    Xia Shengjie; Ni Zheming Xu Qian; Hu Baoxiang; Hu Jun

    2008-10-15

    Zn/Al layered double hydroxides (LDHs) were intercalated with the anionic antihypertensive drugs Enalpril, Lisinopril, Captopril and Ramipril by using coprecipitation or ion-exchange technique. TG-MS analyses suggested that the thermal stability of Ena{sup -}, Lis{sup -} (arranged with monolayer, resulted from X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) analysis was enhanced much more than Cap{sup -} and Ram{sup -} (arranged with bilayer). The release studies show that the release rate of all samples markedly decreased in both pH 4.25 and 7.45. However, the release time of Ena{sup -}, Lis{sup -} were much longer compared with Cap{sup -}, Ram{sup -} in both pH 4.25 and 7.45, it is possible that the intercalated guests, arranged with monolayer in the interlayer, show lesser repulsive force and strong affinity with the LDH layers. And the release data followed both the Higuchi-square-root law and the first-order equation well. Based on the analysis of batch release, intercalated structural models as well as the TG-DTA results, we conclude that for drug-LDH, stronger the affinity between intercalated anions and the layers is, better the thermal property and the stability to the acid attack of drug-LDH, and the intercalated anions are easier apt to monolayer arrangement within the interlayer, were presented. - Graphical abstract: A series of antihypertensive drugs including Enalpril, Lisinopril, Captopril and Ramipril were intercalated into Zn/Al-NO{sub 3}-LDHs successfully by coprecipitation or ion-exchange technique. We focus on the structure, thermal property and low/controlled release property of as-synthesized drug-LDH composite intended for the possibility of applying these LDH-antihypertensive nanohybrids in drug delivery and controlled release systems.

  14. From anion receptors to transporters.

    PubMed

    Gale, Philip A

    2011-03-15

    Cystic fibrosis is the most well-known of a variety of diseases termed channelopathies, in which the regulation of ion transport across cell membranes is so disrupted that the threshold of a pathology is passed. The human toll exacted by these diseases has led a number of research groups, including our own, to create compounds that mediate ion transport across lipid bilayers. In this Account, we discuss three classes of synthetic compounds that were refined to bind and transport anions across lipid bilayer membranes. All of the compounds were originally designed as anion receptors, that is, species that would simply create stable complexes with anions, but were then further developed as transporters. By studying structurally simple systems and varying their properties to change the degree of preorganization, the affinity for anions, or the lipophilicity, we have begun to rationalize why particular anion transport mechanisms (cotransport or antiport processes) occur in particular cases. For example, we have studied the chloride transport properties of receptors based on the closely related structures of isophthalamide and pyridine-2,6-dicarboxamide: the central ring in each case was augmented with pendant methylimidazole groups designed to cotransport H(+) and Cl(-). We observed that the more preorganized pyridine-based receptor was the more efficient transporter, a finding replicated with a series of isophthalamides in which one contained hydroxyl groups designed to preorganize the receptor. This latter class of compound, together with the natural product prodigiosin, can transport bicarbonate (as part of a chloride/bicarbonate antiport process) across lipid bilayer membranes. We have also studied the membrane transport properties of calix[4]pyrroles. Although the parent meso-octamethylcalix[4]pyrrole functions solely as a Cs(+)/Cl(-) cotransporter, other compounds with increased anion affinities can function through an antiport process. One example is octafluoro

  15. Zinc hydroxide stimulates superoxide production by rat alveolar macrophages.

    PubMed

    Ogino, K; Izumi, Y; Ishiyama, H; Murata, T; Kobayashi, H; Houbara, T

    1992-06-30

    The effect of zinc hydroxide on superoxide (O2-) production by rat alveolar macrophages was determined by chemiluminescence and by cytochrome c reduction. Zinc ions had no effect on the chemiluminescence of unstimulated alveolar macrophages. By contrast, zinc hydroxide (ZnOH2), a neutralized form of zinc ions, increased the chemiluminescence level and O2- release. Increased O2- release was inhibited by pertussis toxin, isoquinoline sulfonamide and pretreatment with EGTA. These findings indicate that zinc hydroxide formation from zinc compounds can stimulate the O2- production by alveolar macrophages by receptor-mediated and Ca(2+)-dependent process.

  16. [Development of a visible light-curing calcium hydroxide cement].

    PubMed

    Zhao, Xin-Yi; Kang, Biao; Liu, Han

    2005-05-01

    A visible light-curing calcium hydroxide cement is presented here and the effects of its resin matrix on the Ca2+ releasing, compressive strength of set material and the pH value of water in which set materials immersed are evaluated. Experimental results show that the effects of the selected resin matrix on Ca2+ releasing, compressive strength and pH value are significant. The calcium hydroxide cement containing BEMA or EMA and HEMA as resin matrix has good properties. The pulp capping test showed that an excellent dentin bridge appeared in dogs capped teeth at 70 days. pulp, pulp capping, calcium hydroxide, visible light-curing, dental materials

  17. Nickel hydroxide/cobalt-ferrite magnetic nanocatalyst for alcohol oxidation.

    PubMed

    Bhat, Pooja B; Inam, Fawad; Bhat, Badekai Ramachandra

    2014-08-11

    A magnetically separable, active nickel hydroxide (Brønsted base) coated nanocobalt ferrite catalyst has been developed for oxidation of alcohols. High surface area was achieved by tuning the particle size with surfactant. The surface area of 120.94 m2 g(-1) has been achieved for the coated nanocobalt ferrite. Improved catalytic activity and selectivity were obtained by synergistic effect of transition metal hydroxide (basic hydroxide) on nanocobalt ferrite. The nanocatalyst oxidizes primary and secondary alcohols efficiently (87%) to corresponding carbonyls in good yields.

  18. 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. Copyright © 2012 Elsevier Inc. All rights reserved.

  19. Preparation and performance evaluation of novel alkaline stable anion exchange membranes

    NASA Astrophysics Data System (ADS)

    Irfan, Muhammad; Bakangura, Erigene; Afsar, Noor Ul; Hossain, Md. Masem; Ran, Jin; Xu, Tongwen

    2017-07-01

    Novel alkaline stable anion exchange membranes are prepared from various amounts of N-methyl dipicolylamine (MDPA) and brominated poly (2,6-dimethyl-1,4-phenylene oxide) (BPPO). The dipicolylamine and MDPA are synthesized through condensation reaction and confirmed by 1H NMR spectroscopy. The morphologies of prepared membranes are investigated by atomic force microscopy (AFM), fourier transform infrared spectroscopy (FTIR), 1H NMR spectroscopy and scanning electron microscopy (SEM). The electrochemical and physical properties of AEMs are tested comprising water uptake (WU), ion exchange capacity (IEC), alkaline stability, linear expansion ratio (LER), thermal stability and mechanical stability. The obtained hydroxide conductivity of MDPA-4 is 66.5 mS/cm at 80 °C. The MDPA-4 membrane shows good alkaline stability, high hydroxide conductivity, low methanol permeability (3.43 × 10-7 cm2/s), higher selectivity (8.26 × 107 mS s/cm3), less water uptake (41.1%) and lower linear expansion (11.1%) despite of high IEC value (1.62 mmol/g). The results prove that MDPA membranes have great potential application in anion exchange membrane fuel cell.

  20. Facile surface modification of anion-exchange membranes for improvement of diffusion dialysis performance.

    PubMed

    Kim, Do-Hyeong; Park, Han-Sol; Seo, Seok-Jun; Park, Jin-Soo; Moon, Seung-Hyeon; Choi, Young-Woo; Jiong, Young Su; Kim, Dong Hee; Kang, Moon-Sung

    2014-02-15

    In this study, a facile membrane modification method by spin-coating of pyrrole (Py) monomers dissolved in a volatile solvent followed by an interfacial polymerization is proposed. The surface of a commercial anion-exchange membrane (i.e., Neosepta-AFX, Astom Corp., Japan) was successfully modified with polypyrrole (Ppy) to improve the acid recovery performance in diffusion dialysis (DD). The result of DD experiments revealed that both the acid and metal ion transports are significantly influenced by the surface modification. The metal crossover through the membranes was largely reduced while mostly maintaining the acid permeability by introducing a thin Ppy layer with excellent repelling property to cations on the membrane surface. As a result, the anion-exchange membrane modified with the optimum content of Py monomer (5 vol.%) exhibited excellent acid dialysis coefficient (KAcid) and selectivity (KAcid/KMetal) which is approximately twice as high as that of the pristine membrane. Copyright © 2013 Elsevier Inc. All rights reserved.

  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 Shear Rheology of Coffee Samples

    NASA Astrophysics Data System (ADS)

    Läuger, Jörg; Heyer, Patrick

    2008-07-01

    Both oscillatory and rotational measurements on the film formation process and on interfacial rheological properties of the final film of coffee samples with different concentrations are presented. As higher the concentration as faster the film formation process is, whereas the concentration does not have a large effect on the visco-elastic properties of the final films. Two geometries, a biconical geometry and a Du Noüy ring have been employed. The presented results show that interfacial shear rheology allows detailed investigations on coffee films. Although with a Du Noüy ring it is possible to measure the qualitative behavior and relative differences only the biconical geometry is sensitive enough to test weak films and to reveal real absolute values for the interfacial shear rheological quantities.

  3. Magneto-ionic control of interfacial magnetism.

    PubMed

    Bauer, Uwe; Yao, Lide; Tan, Aik Jun; Agrawal, Parnika; Emori, Satoru; Tuller, Harry L; van Dijken, Sebastiaan; Beach, Geoffrey S D

    2015-02-01

    In metal/oxide heterostructures, rich chemical, electronic, magnetic and mechanical properties can emerge from interfacial chemistry and structure. The possibility to dynamically control interface characteristics with an electric field paves the way towards voltage control of these properties in solid-state devices. Here, we show that electrical switching of the interfacial oxidation state allows for voltage control of magnetic properties to an extent never before achieved through conventional magneto-electric coupling mechanisms. We directly observe in situ voltage-driven O(2-) migration in a Co/metal-oxide bilayer, which we use to toggle the interfacial magnetic anisotropy energy by >0.75 erg cm(-2) at just 2 V. We exploit the thermally activated nature of ion migration to markedly increase the switching efficiency and to demonstrate reversible patterning of magnetic properties through local activation of ionic migration. These results suggest a path towards voltage-programmable materials based on solid-state switching of interface oxygen chemistry.

  4. Magneto-ionic control of interfacial magnetism

    NASA Astrophysics Data System (ADS)

    Bauer, Uwe; Yao, Lide; Tan, Aik Jun; Agrawal, Parnika; Emori, Satoru; Tuller, Harry L.; van Dijken, Sebastiaan; Beach, Geoffrey S. D.

    2015-02-01

    In metal/oxide heterostructures, rich chemical, electronic, magnetic and mechanical properties can emerge from interfacial chemistry and structure. The possibility to dynamically control interface characteristics with an electric field paves the way towards voltage control of these properties in solid-state devices. Here, we show that electrical switching of the interfacial oxidation state allows for voltage control of magnetic properties to an extent never before achieved through conventional magneto-electric coupling mechanisms. We directly observe in situ voltage-driven O2- migration in a Co/metal-oxide bilayer, which we use to toggle the interfacial magnetic anisotropy energy by >0.75 erg cm-2 at just 2 V. We exploit the thermally activated nature of ion migration to markedly increase the switching efficiency and to demonstrate reversible patterning of magnetic properties through local activation of ionic migration. These results suggest a path towards voltage-programmable materials based on solid-state switching of interface oxygen chemistry.

  5. Electrochemical screening of organic and inorganic inhibitors for the corrosion of ASTM A-470 steel in concentrated sodium hydroxide solution

    SciTech Connect

    Moccari, A.; MacDonald, D.D.

    1985-05-01

    The corrosion of ASTM A-470 turbine disk steel in concentrated sodium hydroxide solution (10 mol/kg) containing sodium silicate, sodium dihydrogen phosphate, sodium chromate, aniline and some of its derivatives, tannic acid, L-(-)-phenylalanine (aminopropionic acid) and octadecylamine as potential inhibitors has been studied using the potentiodynamic, AC impedance, and Tafel extrapolation techniques. All tests were performed at 115 + or - 2 C. The anodic and cathodic polarization data show that aniline and its derivatives, L-(-)-phenylalanine, NaH/sub 2/PO/sub 4/, Na/sub 2/SiO/sub 3/, and Na/sub 2/CrO/sub 4/ inhibit the anodic process, whereas tannic acid inhibits the cathodic reaction. Octadecylamine was found to inhibit both the anodic and cathodic processes. The mechanisms of inhibition for some of these compounds have been inferred from the wide band width frequency dispersions of the interfacial impedance.

  6. Homogeneous Precipitation of Nickel Hydroxide Powders

    SciTech Connect

    Mavis, Bora

    2003-01-01

    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 Ni2+ 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 Ni2+ form strong complexes with ammonia presents a challenge in the full recovery of the Ni2+. On the other hand, presence of Al3+ facilitates the complete precipitation of Ni2+ 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™, Version 1.01) lets the user change

  7. Product development of FGD recovered magnesium hydroxide

    SciTech Connect

    Beeghly, J.H.; Babu, M.; Smith, K.J.

    1999-07-01

    The ThioClear FGD processes developed by the Dravo Lime Company (DLC) produce a high brightness gypsum and magnesium hydroxide (Mg(OH){sub 2}) by-product. Both originate as white precipitates from a solution of magnesium sulfate. The use of magnesium-enhanced lime avoids the mineral impurities from direct neutralization when using pulverized limestone rock. White, pure FGD synthetic gypsum can be used to produce higher value products such as mineral fillers and industrial plasters. This paper focuses on the product development of the Mg(OH){sub 2} by-product. Commercial Mg(OH){sub 2} sells at over $200/Ton for a variety of uses, most of which is wastewater treatment and a feedstock to make magnesium chemicals and refractories. Beneficial uses in the power plant are pH control of acidic coal pile stormwater runoff and bottom ash quench water. A future use being explored is injection into coal fired boilers to neutralize sulfur trioxide (SO{sub 3}) to prevent stack gas opacity related emission problems and minimize air preheater corrosion and fouling. The objective of this project is to improve the purity and solids content of the by-product after it is separated from the gypsum. Several options were investigated to convert it into a more marketable or usable form. Test results and economic evaluations are reported during the different process steps needed to improve the product quality: (1) dissolving or washing out the gypsum impurity; (2) thickening the washed solids and using the overflow for makeup water within the FGD water balance; (3) finding the best means to dewater the washed, thickened slurry; and (4) repulp the dewatered cake into a stabilized slurry or dry it to powder. Flash drying the dewatered cake is compared to spray drying the thickened slurry. FGD Mg(OH){sub 2} is shown to have equal reactivity as an acid neutralization reagent on a Mg(OH){sub 2} molar basis to commercial Mg(OH){sub 2} products and other alkaline reagents. Its use for pH control

  8. Mephisto: Interfacial Destabilization in Metal Alloys

    NASA Technical Reports Server (NTRS)

    Favier, J. J.; Malmejac, Y.

    1985-01-01

    The destabilizing mechanisms at a solidification interface were studied to obtain information on the kinetics and morphologies in the transient and steady state, and to separate the influences of liquid phase instabilities from interfacial instabilities. A differential seebeck voltage measurements technique was developed to provide a continuous record of the solid-liquid interface temperature as the solidification rate is varied to determine the kinetic coefficients. Signal processing and noise suppression techniques allow nonovolt precision which corresponds to mK accuracy for the interfacial temperature.

  9. 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.

  10. Relationship Between Interfacial Strength and Materials Properties in Hybrid Organic/Inorganic Nanomaterials

    NASA Astrophysics Data System (ADS)

    Snyder, Chad; Richardson, Mickey; Zhou, Jing; Holmes, Gale; Karim, Alamgir; D'Souza, Nandika

    2008-03-01

    Thermal interface materials (TIM's) are critical to the semiconductor electronics industry for heat dissipation, a potential show-stopper for future technology nodes. Essentially, an epoxy nanocomposite, TIMs suffer from a series of typical nanocomposite limitations including heat conduction in nanoscale inclusions, nanoparticle dispersion, void formation with thermal cycling, and interfacial resistance between the matrix and filler. It is postulated that the interfacial adhesion between the matrix and nanofiller is at the root cause of many of these difficulties, however, few techniques exist to characterize this critical property. Compounding this are the overall difficulties associated with characterizing these materials in their ultimate applications, i.e., thin films. To this end, a novel series of organic/inorganic hybrid nanostructured materials based on layered double hydroxides in epoxy matrices were designed as a test bed to develop the measurement techniques needed to elucidate the relationship between the material structure and dynamics and the ultimate materials properties. Initial results are presented based on characterization by mechanical, dielectric, and thermal spectroscopies.

  11. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis.

    PubMed

    Song, Fang; Hu, Xile

    2014-07-17

    The oxygen evolution reaction is a key reaction in water splitting. The common approach in the development of oxygen evolution catalysts is to search for catalytic materials with new and optimized chemical compositions and structures. Here we report an orthogonal approach to improve the activity of catalysts without alternating their compositions or structures. Specifically, liquid phase exfoliation is applied to enhance the oxygen evolution activity of layered double hydroxides. The exfoliated single-layer nanosheets exhibit significantly higher oxygen evolution activity than the corresponding bulk layered double hydroxides in alkaline conditions. The nanosheets from nickel iron and nickel cobalt layered double hydroxides outperform a commercial iridium dioxide catalyst in both activity and stability. The exfoliation creates more active sites and improves the electronic conductivity. This work demonstrates the promising catalytic activity of single-layered double hydroxides for the oxygen evolution reaction.

  12. 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

  13. 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%.

  14. 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.

  15. 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,...

  16. 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,...

  17. 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,...

  18. Studies on the intercalation of naproxen into layered double hydroxide and its thermal decomposition by in situ FT-IR and in situ HT-XRD

    NASA Astrophysics Data System (ADS)

    Wei, Min; Shi, Shuxian; Wang, Ji; Li, Yong; Duan, Xue

    2004-07-01

    Layered double hydroxides, novel anionic clay, meet the first requirement as inorganic matrices for encapsulating functional drugs or biomolecules with negative charge in aqueous media. In this study, naproxen has been intercalated into Mg-Al layered double hydroxide by the methods of ion exchange. The structure and composition of the intercalated material have been studied by X-ray diffraction (XRD), UV-vis spectroscopy and inductively coupled plasma emission spectroscopy. A schematic model has been proposed. Furthermore, in situ Fourier transform infrared spectroscopy, in situ high-temperature XRD, and thermogravimetry (TG) have been used to characterize the thermal decomposition of the hybrid material. It has been found that the thermal stability of the intercalated naproxen is significantly enhanced compared with the pure form before intercalation, which suggests that this drug-inorganic layered material may have prospective application as the basis of a novel drug delivery system.

  19. Vibrational Autodetachment in Nitroalkane Anions

    NASA Astrophysics Data System (ADS)

    Adams, Christopher L.; Weber, J. Mathias

    2010-06-01

    Nitroalkanes have electron affinities ge 1370 cm-1, well below the excitation energies for CH stretching modes, with the excess charge localized on the nitro group. Upon absorption of an IR photon in a CH stretching vibrational mode, the absorbed energy is redistributed in the molecule. If enough energy is transferred to the NO2 stretching/wagging modes, the excess electron residing on the nitro group is emitted. Vibrational autodetachment (VAD) spectra encode information regarding intramolecular vibrational relaxation (IVR) processes leading up to electron emission. We present VAD photoelectron spectroscopy of polyatomic molecular anions and discuss how a VAD photoelectron spectrum can be modeled.

  20. Molecular Scale Description of Anion Competition on Amine-Functionalized Surfaces.

    PubMed

    Rock, William; Oruc, Muhammed E; Ellis, Ross J; Uysal, Ahmet

    2016-11-08

    Many industrial and biological processes involve the competitive adsorption of ions with different valencies and sizes at charged surfaces; heavy and precious metal ions are separated on the basis of their propensity to adsorb onto interfaces, often as anionic ion clusters (e.g., [MClx](n-)). However, very little is known, both theoretically and experimentally, about the competition of factors that drive preferential adsorption, such as charge density or valence, at interfaces in technologically relevant systems. There are even contradictory pictures described by interfacial studies and real life applications, such as chlorometalate extractions, in which charge diffuse chlorometalate ions are extracted efficiently even though charge dense chloride ions present in the background are expected to occupy the interface. We studied the competition between divalent chlorometalate anions (PtCl6(2-) and PdCl4(2-)) and monovalent chloride anions on positively charged amine-functionalized surfaces using in situ specular X-ray reflectivity. Chloride anions were present in vast excess to simulate the conditions used in the commercial separation of heavy and precious metal ions. Our results suggest that divalent chlorometalate adsorption is a two-step process and that the divalent anions preferentially adsorb at the interface despite having a charge/volume ratio lower than that of chloride. These results provide fundamental insight into the structural mechanisms that underpin transport in phases that are relevant to heavy and precious metal ion separations, explaining the high efficiency of low charge density ion transport processes in the presence of charge dense anions.