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Sample records for bulky rhodium intercalators

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

    International Nuclear Information System (INIS)

    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. - Graphical abstract: The Eu3+-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. • Eu3+-doping led to red luminescence from the hydroxides in association with the intercalated organic anions

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

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Mebae; Fujihara, Shinobu, E-mail: shinobu@applc.keio.ac.jp

    2014-02-15

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

  3. Measuring bulky waste arisings in Hong Kong

    International Nuclear Information System (INIS)

    All too often, waste authorities either assume that they know enough about their bulky waste stream or that it is too insignificant to deserve attention. In this paper, we use Hong Kong as an example to illustrate that official bulky waste figures can actually be very different from the reality and therefore important waste management decisions made based on such statistics may be wrong too. This study is also the first attempt in Hong Kong to outline the composition of bulky waste. It was found that about 342 tonnes/day of wood waste were omitted by official statistics owing to incomplete records on actual bulky waste flow. This is more than enough to provide all the feedstock needed for one regular-sized wood waste recycling facility in Hong Kong. In addition, the proportion of bulky waste in the municipal solid waste (MSW) streams in Hong Kong should be about 6.1% instead of the officially stated 1.43%. Admittedly, there are limitations with this study. Yet, present findings are suggestive of significant MSW data distortion in Hong Kong.

  4. Study on the Recovery of Rhodium from Spent Organic Rhodium Catalysts of Acetic Acid Industry Using Pyrometallurgical Process

    Institute of Scientific and Technical Information of China (English)

    HE Xiaotang; WANG Huan; WU Xilong; LI Yong; ZHAO Yu; HAN Shouli; LI Kun; GUO Junmei

    2012-01-01

    A new process recycling rhodium from organic waste containing rhodium in acetic acid industry is developed.Use the special affinity of base metal sulfides (FeS,Ni2S3,CuS,etc.) on platinum group metals,adopting high nickel matte trapping-aluminothermic activation method to recovery rhodium from incinerator residue of organic rhodium waste.The method is shorter process,lower equipment requirement,and the higher activity of rhodium black.In pyrometallurgy enrichment process,the recovery rate of rhodium reached 94.65%,the full flow of rhodium recovery rate was 92.04%.

  5. Graphite intercalation compounds and applications

    CERN Document Server

    Enoki, Toshiaki; Endo, Morinobu

    2003-01-01

    1. Introduction. 2. Synthesis and Intercalation Chemistry. 3. Structures and Phase Transitions. 4. Lattice Dynamics. 5. Electronic Structures. 6. Electron Transport Properties. 7. Magnetic Properties. 8. Surface Properties and Gas Adsorption. 9. GICs and Batteries. 10. Highly Conductive Graphite Fibers. 11. Exfoliated Graphite Formed by Intercalation. 12. Intercalated Fullerenes and Carbon Nanotubes. Index

  6. Structural studies of intercalants

    Energy Technology Data Exchange (ETDEWEB)

    Hastings, J.B.

    1981-01-01

    The structure of stage 2 potassium intercalated graphite, KC/sub 24/, is discussed in both the ordered and disordered phases. A one-dimensional model is used to illustrate the qualitative features of the KC/sub 24/ diffraction patterns.

  7. Bulky waste quantities and treatment methods in Denmark

    DEFF Research Database (Denmark)

    Larsen, Anna Warberg; Petersen, Claus; Christensen, Thomas Højlund

    2012-01-01

    Bulky waste is a significant and increasing waste stream in Denmark. However, only little research has been done on its composition and treatment. In the present study, data about collection methods, waste quantities and treatment methods for bulky waste were obtained from two municipalities....... In addition a sorting analysis was conducted on combustible waste, which is a major fraction of bulky waste in Denmark. The generation of bulky waste was found to be 150–250 kg capita−1 year−1, and 90% of the waste was collected at recycling centres; the rest through kerbside collection. Twelve main fractions...... were identified of which ten were recyclable and constituted 50–60% of the total quantity. The others were combustible waste for incineration (30–40%) and non-combustible waste for landfilling (10%). The largest fractions by mass were combustible waste, bricks and tile, concrete, non-combustible waste...

  8. Intercalation Assembly Method and Intercalation Process Control of Layered Intercalated Functional Materials

    Institute of Scientific and Technical Information of China (English)

    LI Kaitao; WANG Guirong; LI Dianqing; LIN Yanjun; DUAN Xue

    2013-01-01

    Layered intercalated functional materials of layered double hydroxide type are an important class of functional materials developed in recent years.Based on long term studies on these materials in the State Key Laboratory of Chemical Resource Engineering in Beijing University of Chemical Technology,the principle for the design of controlled intercalation processes in the light of future production processing requirements has been developed.Intercalation assembly methods and technologies have been invented to control the intercalation process for preparing layered intercalated materials with various structures and functions.

  9. Rhodium-Catalyzed Decarbonylation of Aldoses

    DEFF Research Database (Denmark)

    Monrad, Rune; Madsen, Robert

    2007-01-01

    A catalytic procedure is described for decarbonylation of unprotected aldoses to afford alditols with one less carbon atom. The reaction is performed with the rhodium complex Rh(dppp)2Cl in a refluxing diglyme - DMA solution. A slightly improved catalyst turnover is observed when a catalytic amou...

  10. Rhodium olefin complexes of diiminate type ligands

    NARCIS (Netherlands)

    Willems, Sander Theodorus Hermanus

    2003-01-01

    The mono-anionic beta-diiminate ligand (ArNC(CH3)CHC(CH3)NAr) on several previous occasions proved useful in stabilising low coordination numbers for both early and late transition metals. In this thesis the reactivity of the rhodium olefin complexes of one of these beta-diiminate ligands (Ar = 2,6-

  11. Carbon nanofiber growth on thin rhodium layers

    NARCIS (Netherlands)

    Chinthaginjala, J.K.; Unnikrishnan, S.; Smithers, M.A.; Kip, G.A.M.; Lefferts, L.

    2012-01-01

    A thinlayer of carbon nanofibers (CNFs) was synthesized on a thin polycrystalline rhodium (Rh) metal layer by decomposing ethylene in the presence of hydrogen. Interaction of Rh crystals with carbon results in fragmentation and formation of Rh-nanoparticles, facilitating CNF growth. CNFs are immobil

  12. Chemical modification of niobium layered oxide by tetraalkylammonium intercalation

    International Nuclear Information System (INIS)

    Chemical modification of the layered K4Nb6O17 material was systematically investigated through the reaction of its proton-exchanged form (H2K2Nb6O17) in alkaline solutions containing tetramethylammonium (tma+), tetraethylammonium (tea+) or tetrapropylammonium (tpa+) cations. The intercalated amount reaches 50% (for tma+), 25% (for tea+) and 15% (for tpa+) of the H2K2Nb6O17 negative charge (concerning the exchange at interlayer I) due to the steric hindrance of larger cations. Hexaniobate samples present (020) basal reflections equal to 23.0, 26.3 and 26.5 A once intercalated respectively with tma+, tea+ and tpa+. When samples are heated above 200-250 deg C, CO2 evolution is observed; Hofmann elimination reaction is also detected for hexaniobate-tpa+ samples. Scanning electron microscopy images show the predominance of plate-like particles; stick-like particles are also observed for samples containing bulky ions. The intercalation reaction is promoted in the order tma+ > tea+ > tpa+, while the formation of a dispersion of colloidal particles is facilitated in the inverse order. (author)

  13. Aluminum Dimer Containing Bulky 1,2,3-Triazolate Ligand

    Directory of Open Access Journals (Sweden)

    Issam Kobrsi

    2014-01-01

    Full Text Available The first molecular aluminum 1,2,3-triazolato complex was synthesized bearing a bulky 1,2,3-triazolate ligand. Oligomers and polymers were avoided due to the bulkiness and noncoordinating nature of the substituents. The novel Al2N4 ring formed contains symmetrical Al-N bond distances unexpectedly having asymmetric Al-N-N angles of 144.55(15° and 115.83(14°. This asymmetry demonstrates the effect of the steric hindrance of the ligand.

  14. DPZ-1M rhodium neutron detector performance

    International Nuclear Information System (INIS)

    The characteristics of the DPZ-1M rhodium self-powered neutron detector based on the calculational technique using corrected experimental data are given. These detectors are used for power distribution monitoring in the WWER reactors. For calculating neutron absorption in an emitter incident neutron flux is specified, while the probability of β-particles escape is determined on the base of empirical dependence of extrapolated electron path on its energy. In addition correction by the emither radius of the probability distribution of β-particles escape by experimental data is performed. The results obtained permit to conclude that the rhodium detector possesses high sensitivity to epithermal neutrons Which depends on the neutron spectrum form; current relation of burned-up and non burned- up detector seightly depends on the spectrum form, neutron gas temperature and average neutron spectral hardness

  15. Solid state phase detector replaces bulky transformer circuit

    Science.gov (United States)

    Moberly, C. L.

    1967-01-01

    Miniature solid state phase detector using MOSFETs is used in a phase lock loop with a sun-bit detector in an integrated data-link circuit. This replaces bulky transformer circuits. It uses an inverter amplifier, a modulator switch, and a buffer amplifier.

  16. ASYMMETRIC HYDROSILYLATION CATALYZED BY POLYMER—SUPPORTED THIAZOLIDINE RHODIUM CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    LEIYanohui; LIHong; 等

    1999-01-01

    Asymmetric hydrisilylation catalyzed by polymeric thiazolidine rhodium catalysts was conducted.Almost the same optical yields have been obtained when comb-shaped polymeric ligands and their corresponding monomer complexed rhodium cataltysts were used to asymmetric hydrosilylation of acetophenone.Optical yield of chiral 1-methylbenzyl alcohol reaches as high as 71.5%.Temperature dependence of enantioselective hydrosilylation of acetophenone was discussed.

  17. Adhesion of rhodium films on metallic substrates

    Energy Technology Data Exchange (ETDEWEB)

    Marot, L. [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland)], E-mail: laurent.marot@unibas.ch; Covarel, G.; Tuilier, M.-H. [Laboratoire Mecanique, Materiaux et Procedes de Fabrication, Pole STIC-SPI-Math 61 rue Albert Camus, Universite de Haute-Alsace, F-68093 - Mulhouse Cedex (France); Steiner, R.; Oelhafen, P. [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland)

    2008-09-01

    Rhodium coated metallic films were prepared by magnetron sputtering on metallic substrates. All films were elaborated in same conditions on copper, molybdenum and stainless steel. Adhesion strength tests were carried out by scratch test. The results reveal that the adhesion strength between the film and the substrate is influenced by the hardness of the substrate. Increase of deposition temperature improves the adhesion of the coating. In addition, pre-treatment of substrates by a filtered cathodic vacuum arc and the layer thickness have has some effects on the final adhesion strength.

  18. Structural properties of small rhodium clusters

    Energy Technology Data Exchange (ETDEWEB)

    Soon, Yee Yeen; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    We report a systematic study of the structural properties of rhodium clusters at the atomistic level. A novel global-minimum search algorithm, known as parallel tempering multicanonical basin hopping plus genetic algorithm (PTMBHGA), is used to obtain the geometrical structures with lowest minima at the semi-empirical level where Gupta potential is used to describe the atomic interaction among the rhodium atoms. These structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA). The structures are optimized for different spin multiplicities. The ones with lowest energies will be taken as ground-state structures. In most cases, we observe only minor changes in the geometry and bond length of the clusters as a result of DFT-level re-optimization. Only in some limited cases, the initial geometries obtained from the PTMBHGA are modified by the re-optimization. The variation of structural properties, such as ground-state geometry, symmetry and binding energy, with respect to the cluster size is studied and agreed well with other results available in the literature.

  19. Structural properties of small rhodium clusters

    Science.gov (United States)

    Soon, Yee Yeen; Lim, Thong Leng; Yoon, Tiem Leong

    2015-04-01

    We report a systematic study of the structural properties of rhodium clusters at the atomistic level. A novel global-minimum search algorithm, known as parallel tempering multicanonical basin hopping plus genetic algorithm (PTMBHGA), is used to obtain the geometrical structures with lowest minima at the semi-empirical level where Gupta potential is used to describe the atomic interaction among the rhodium atoms. These structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA). The structures are optimized for different spin multiplicities. The ones with lowest energies will be taken as ground-state structures. In most cases, we observe only minor changes in the geometry and bond length of the clusters as a result of DFT-level re-optimization. Only in some limited cases, the initial geometries obtained from the PTMBHGA are modified by the re-optimization. The variation of structural properties, such as ground-state geometry, symmetry and binding energy, with respect to the cluster size is studied and agreed well with other results available in the literature.

  20. Photoelectron Spectroscopy of Intercalation Phases

    OpenAIRE

    Wu, Qi-Hui

    2003-01-01

    V2O5 and LiMn2O4 are promising cathode materials for lithium-ion batteries due to their high capacities and battery voltages. The several work was mainly focused on the study of electrochemical and structural properties during lithium intercalation. But there is no detailed knowledge of the changes in electronic structure and the intercalation mechanism itself. Especially no general agreement has been reached on the nature and the extent of the interactions between host material and alkali gu...

  1. Aberration corrected STEM of iron rhodium nanoislands

    Science.gov (United States)

    McLaren, M. J.; Hage, F. S.; Loving, M.; Ramasse, Q. M.; Lewis, L. H.; Marrows, C. H.; Brydson, R. M. D.

    2014-06-01

    Iron-rhodium (FeRh) nanoislands of equiatomic composition have been analysed using scanning transmission electron microscopy (STEM) electron energy loss spec-troscopy(EELS) and high angle annular dark field (HAADF) techniques. Previous magne-tometry results have lead to a hypothesis that at room temperature the core of the islands are antiferromagnetic while the shell has a small ferromagnetic signal. The causes of this effect are most likely to be a difference in composition at the edges or a strain on the island that stretches the lattice and forces the ferromagnetic transition. The results find, at the film-substrate interface, an iron-rich layer ~ 5 Å thick that could play a key role in affecting the magnetostructural transition around the interfacial region and account for the room temperature ferromagnetism.

  2. Ca intercalated bilayer graphene as a thinnest limit of superconducting C6Ca.

    Science.gov (United States)

    Kanetani, Kohei; Sugawara, Katsuaki; Sato, Takafumi; Shimizu, Ryota; Iwaya, Katsuya; Hitosugi, Taro; Takahashi, Takashi

    2012-11-27

    Success in isolating a 2D graphene sheet from bulky graphite has triggered intensive studies of its physical properties as well as its application in devices. Graphite intercalation compounds (GICs) have provided a platform of exotic quantum phenomena such as superconductivity, but it is unclear whether such intercalation is feasible in the thinnest 2D limit (i.e., bilayer graphene). Here we report a unique experimental realization of 2D GIC, by fabricating calcium-intercalated bilayer graphene C(6)CaC(6) on silicon carbide. We have investigated the structure and electronic states by scanning tunneling microscopy and angle-resolved photoemission spectroscopy. We observed a free-electron-like interlayer band at the Brillouin-zone center, which is thought to be responsible for the superconductivity in 3D GICs, in addition to a large π* Fermi surface at the zone boundary. The present success in fabricating Ca-intercalated bilayer graphene would open a promising route to search for other 2D superconductors as well as to explore its application in devices.

  3. Superconductivity in graphite intercalation compounds

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert P. [Cavendish Laboratory, University of Cambridge, Madingley Road, Cambridge CB3 0HE (United Kingdom); Weller, Thomas E.; Howard, Christopher A. [Department of Physics & Astronomy, University College of London, Gower Street, London WCIE 6BT (United Kingdom); Dean, Mark P.M. [Department of Condensed Matter Physics and Materials Science, Brookhaven National Laboratory, Upton, NY 11973 (United States); Rahnejat, Kaveh C. [Department of Physics & Astronomy, University College of London, Gower Street, London WCIE 6BT (United Kingdom); Saxena, Siddharth S. [Cavendish Laboratory, University of Cambridge, Madingley Road, Cambridge CB3 0HE (United Kingdom); Ellerby, Mark, E-mail: mark.ellerby@ucl.ac.uk [Department of Physics & Astronomy, University College of London, Gower Street, London WCIE 6BT (United Kingdom)

    2015-07-15

    Highlights: • Historical background of graphite intercalates. • Superconductivity in graphite intercalates and its place in the field of superconductivity. • Recent developments. • Relevant modeling of superconductivity in graphite intercalates. • Interpretations that pertain and questions that remain. - Abstract: The field of superconductivity in the class of materials known as graphite intercalation compounds has a history dating back to the 1960s (Dresselhaus and Dresselhaus, 1981; Enoki et al., 2003). This paper recontextualizes the field in light of the discovery of superconductivity in CaC{sub 6} and YbC{sub 6} in 2005. In what follows, we outline the crystal structure and electronic structure of these and related compounds. We go on to experiments addressing the superconducting energy gap, lattice dynamics, pressure dependence, and how these relate to theoretical studies. The bulk of the evidence strongly supports a BCS superconducting state. However, important questions remain regarding which electronic states and phonon modes are most important for superconductivity, and whether current theoretical techniques can fully describe the dependence of the superconducting transition temperature on pressure and chemical composition.

  4. Superconductivity in graphite intercalation compounds

    International Nuclear Information System (INIS)

    Highlights: • Historical background of graphite intercalates. • Superconductivity in graphite intercalates and its place in the field of superconductivity. • Recent developments. • Relevant modeling of superconductivity in graphite intercalates. • Interpretations that pertain and questions that remain. - Abstract: The field of superconductivity in the class of materials known as graphite intercalation compounds has a history dating back to the 1960s (Dresselhaus and Dresselhaus, 1981; Enoki et al., 2003). This paper recontextualizes the field in light of the discovery of superconductivity in CaC6 and YbC6 in 2005. In what follows, we outline the crystal structure and electronic structure of these and related compounds. We go on to experiments addressing the superconducting energy gap, lattice dynamics, pressure dependence, and how these relate to theoretical studies. The bulk of the evidence strongly supports a BCS superconducting state. However, important questions remain regarding which electronic states and phonon modes are most important for superconductivity, and whether current theoretical techniques can fully describe the dependence of the superconducting transition temperature on pressure and chemical composition

  5. The extraction of trichlorostannato-rhodium complexes by polyurethane foam

    International Nuclear Information System (INIS)

    Polyurethane foam (polyether based) has been found to efficiently extract rhodium from hydrochloric acid solutions containing stannous chloride. The amount of rhodium extracted is significantly influenced by inter alia temperature, acid concentration, the Sn(II):Rh mol ratio and the presence of alkali metal cations. The extraction efficiency is promoted by increased acid concentration and high Sn(II):Rh ratios. The presence of K+ inhibits the extraction or rhodium, while the effect of Li+ and Na+ is small. A series of model urethane compounds (diurethane podands and linear polyurethanes) have been synthesized and characterized. These model compounds allowed the direct determination of the extracted trichlorostannato-rhodium complex anions by 119Sn nmr spectroscopy. The 119Sn nmr study showed the formation of a new rhodium-hydrido complex formulated to be [RhH(SnCl3)4Cl]3-. In the presence of low tin(II) concentrations (Sn(II):Rh = 4:1), [Rh(SnCl3)3Cl3]3- is predominantly extracted by the foam phase. Analysis of the acid-decomposed polyurethane foam phase by atomic absorption spectroscopy and of the model urethane compound phase by 7Li nmr spectroscopy, confirmed the extraction of alkali metal cations from aqueous solutions containing alkali metal salts. It is indicated that the polyether chains of polyurethane foam play a major role in the extraction process, and that the flexibility of the chains influences the efficiency of polyurethane foam as an extractant. The creation of cationic sites within the foam matrix, which facilitate the extraction of the rhodium-tin complex anions, is postulated to occur by protonation of the donor oxygen atoms as well as by chelation of cations such as H3O+, Li+, Na+ and K+ by the polyether chains. A working model for the extraction of the trichlorostannato-rhodium complexes by polyurethane foam is proposed. 79 figs., 51 tabs., 272 refs

  6. Synthesis and Reactivity of a Transient, Terminal Nitrido Complex of Rhodium

    NARCIS (Netherlands)

    M.G. Scheibel; Y. Wu; A.C. Stückl; L. Krause; E. Carl; D. Stalke; B. de Bruin; S. Schneider

    2013-01-01

    Irradiation of rhodium(II) azido complex [Rh(N3){N(CHCHPtBu2)2}] allowed for the spectroscopic characterization of the first reported rhodium complex with a terminal nitrido ligand. DFT computations reveal that the unpaired electron of rhodium(IV) nitride complex [Rh(N){N(CHCHPtBu2)2}] is located in

  7. Reduction of nitric oxide over platinum, rhodium and platinum-rhodium single crystal surfaces. Doctoral thesis

    Energy Technology Data Exchange (ETDEWEB)

    Siera, J.

    1992-11-11

    Although platinum and rhodium are introduced separately in the three-way catalyst, it is established that Pt-Rh alloy particles are formed during its performance. Despite the widespread use of the three-way catalyst and the intensive research on the catalytic properties of the pure metals, relatively little is known about the alloy system. In the thesis results are described for the NO-H2, NO-NH3, CO-O2 and CO-NO reactions on the surfaces of Pt, Rh and Pt-Rh alloy single crystals.

  8. Preparation and Properties of Phenolic Resin/Montmorillonite Intercalation Nanocomposites

    Institute of Scientific and Technical Information of China (English)

    YU Jian-ying; WEI Lian-qi; CAO Xian-kun

    2003-01-01

    Phenolic resin/ montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation. Properties and structure of the composites were investigated by using XRD , TG and test of softening point. It is indicated that both the pressing intercalation and melt intercalation can be used to prepare the phenolic resin/organo-montmorillonite intercalation nanocomposites. Compared with phenolic resin, the intercalation nanocomposites have better heat-resistance, higher decomposition temperatures and less thermal weight-loss. However , these two intercalation methods have different effects on the softening point of the intercalation nanocomposites . Pressing intercalation almost does not affect the softening point of the intercalation nanocomposites, while melt intercalation signifwantly increases the softening point of the intercalation nanocomposites ,probably due to the chemical actions happening in the process of melt intercalation.

  9. Size control of rhodium particles of silica-supported catalysts using water-in-oil microemulsion

    Science.gov (United States)

    Kishida, Masahiro; Hanaoka, Toshiaki; Kim, Won Young; Nagata, Hideo; Wakabayashi, Katsuhiko

    1997-11-01

    Effects of components of water-in-oil microemulsions on rhodium particle sizes of silica-supported rhodium catalysts were investigated in the catalyst preparation method using microemulsion. In the case of the microemulsion of polyoxyethylene(23)dodecyl ether/ n-alcohols/RhCl 3 aq., the rhodium particle size increased from 3.4 to 5.0 nm as the specific permittivity of the organic solvent increased. The chain length of hydrophilic group of polyoxyethylene- p-nonylphenyl ether ( n = 5 to 15) employed as surfactants had an effect on the rhodium particle size where the rhodium size ranged between 2.0 and 3.6 nm. The rhodium particle size was 1.5 nm in the case of sodium bis(2-ethylhexyl) sulfocuccinate and this value was found to be the smallest. These results could be interpreted in terms of the adsorption of the surfactant on rhodium-hydrazine particle surface.

  10. Snapshot analysis for rhodium fixed incore detector using BEACON methodology

    International Nuclear Information System (INIS)

    The purpose of this report is to process the rhodium detector data of the Yonggwang nuclear unit 4 cycle 5 core for the measured power distribution by using the BEACON methodology. Rhodium snapshots of the YGN 4 cycle 5 have been analyzed by both BEACON/SPINOVA and CECOR to compare the results of both codes. By analyzing a large number of snapshots obtained during normal plant operation. Reviewing the results of this analysis, the BEACON/SPNOVA can be used for the snapshot analysis of Korean Standard Nuclear Power (KSNP) plants

  11. Surgical Management of Bulky Mediastinal Metastases in Follicular Thyroid Carcinoma

    Directory of Open Access Journals (Sweden)

    Zainal Adwin

    2016-01-01

    Full Text Available Follicular thyroid adenoma and carcinoma are very common. Benign and malignant lesions are usually indistinguishable from cytology alone and often require confirmatory resection. The spread of follicular carcinoma is usually hematogenous and is treated with surgery and adjuvant radioactive iodine. Very rarely, metastases occur in the mediastinum. Patients usually present with severe compressive symptoms. With proper treatment and follow-up, the prognosis for these type of thyroid malignancies is excellent. In the case presented here, our patient presented to the Universiti Kebangsaan Malaysia Medical Center with a progressively enlarging anterior neck swelling. The swelling had started 10 years before his presentation. We diagnosed him with an advanced thyroid malignancy with bulky mediastinal metastases. After extensive investigations and counseling, we chose to treat the patient with tumor excision and mediastinal metastases resection. Typically, mediastinal resection involves the removal of the sternum and use of an acrylic implant to recreate the sternum. In this case, the sternum and ribs were removed with subsequent myocutaneous flap coverage for the wound defect. Our experience represents an alternative treatment option in cases where implant use is unsuitable.

  12. Tomography of actinides by photofission in bulky radioactive waste packages

    International Nuclear Information System (INIS)

    Quantifying actinides using non-destructive methods, in radioactive waste packages, is a great stake to turn packages towards appropriate storage facility. But the nature of radiations emitted by actinides (alpha radiations) makes the detection of those very difficult for large volume packages characterization. Indeed, the emitted radiation is too weak, either to be detected by emission tomography or to reach required sensitivities. Therefore, it is necessary to turn to an external probing source. Tomography based on detection of delayed neutrons induced by photofission, allows to probe bulky packages. We demonstrate the suitability of this method to an industrial stage. Firstly, we determine and qualify projection matrix which connects measures at reconstructed activity of tomographic picture. Thus, during measurements on a model and a real package, we carry out convincing tomographic reconstructions with real acquisition conditions. More, we prove that it is possible to take all disruptive chemical element into account, for tomographic reconstructions, in order to obtain the best image of activity. So, we propose a finalised tomographic device, integrating a shielding cell, and checking all the activity and distribution activity criterions fixed for acceptance of radioactive waste packages in superficial storage facility. (author)

  13. Selective Electrochemical versus Chemical Oxidation of Bulky Phenol.

    Science.gov (United States)

    Zabik, Nicole L; Virca, Carolyn N; McCormick, Theresa M; Martic-Milne, Sanela

    2016-09-01

    The electrochemical oxidation of selected tert-butylated phenols 2,6-di-tert-butyl-4-methylphenol (1), 2,6-di-tert-butylphenol (2), 2,4,6-tri-tert-butylphenol (3), 2-tert-butylphenol (4), and 4-tert-butylphenol (5) was studied in an aprotic environment using cyclic voltammetry, square-wave voltammetry, and UV-vis spectroscopy. All compounds exhibited irreversible oxidation of the corresponding phenol or phenolate ion. Compound 2 was selectively electrochemically oxidized, while other phenol analogues underwent mostly chemical oxidation. The electrochemical oxidation of 2 produced a highly absorbing product, 3,5,3',5'-tetra-tert-butyl-4,4'-diphenoquinone, which was characterized by X-ray crystal diffraction. The electrochemical oxidation was monitored as a function of electrochemical parameters and concentration. Experimental and theoretical data indicated that the steric hindrance, phenoxyl radical stability, and hydrogen bonding influenced the outcome of the electrochemical oxidation. The absence of the substituent at the para position and the presence of the bulky substituents at ortho positions were structural and electrostatic requirements for the selective electrochemical oxidation.

  14. Intercalation of Amido Cationic Drug with Montmorillonite

    Institute of Scientific and Technical Information of China (English)

    ZHENG Junping; WANG Hongyan; ZHUANG Hong; XI Lifei; YAO Kangde

    2007-01-01

    The intercalation of drug molecules with montmorillonit (MMT) using Acyclovir (ACV) as the model drug was focused on. The optimum conditions were studied based on orthogonal design, such as intercalation time and temperature. The intercalation composites were characterized by X-ray diffraction (XRD), Fourier transformed infrared (FT-IR), and thermogravimetric analysis (TGA). The experimental results reveal that ACV is successfully intercalated into the interlayers of MMT. The in vitro release experiments reveal that ACV is released from MMT steadily and pH dependent

  15. SURFACE STRUCTURE AND COMPOSITION CHANGES ON PLATINUM - RHODIUM ALLOY CATALYSTS

    OpenAIRE

    McCabe, A.; Smith, G.

    1984-01-01

    Platinum-rhodium gauze catalysts used in the manufacture of nitric acid undergo an extensive surface reconstruction process. This has been investigated using a miniature catalytic reactor, FIM atom probe, electron microscopy and X-ray techniques. A mechanism involving vapour transport is proposed to explain the main features of the variation in catalyst behaviour with operating conditions.

  16. Electronic and magnetic properties of small rhodium clusters

    Energy Technology Data Exchange (ETDEWEB)

    Soon, Yee Yeen; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    We report a theoretical study of the electronic and magnetic properties of rhodium-atomic clusters. The lowest energy structures at the semi-empirical level of rhodium clusters are first obtained from a novel global-minimum search algorithm, known as PTMBHGA, where Gupta potential is used to describe the atomic interaction among the rhodium atoms. The structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof generalized gradient approximation. For the purpose of calculating the magnetic moment of a given cluster, we calculate the optimized structure as a function of the spin multiplicity within the DFT framework. The resultant magnetic moments with the lowest energies so obtained allow us to work out the magnetic moment as a function of cluster size. Rhodium atomic clusters are found to display a unique variation in the magnetic moment as the cluster size varies. However, Rh{sub 4} and Rh{sub 6} are found to be nonmagnetic. Electronic structures of the magnetic ground-state structures are also investigated within the DFT framework. The results are compared against those based on different theoretical approaches available in the literature.

  17. Methane Steam Reforming Kinetics for a Rhodium-Based Catalyst

    DEFF Research Database (Denmark)

    Jakobsen, Jon Geest; Jakobsen, M.; Chorkendorff, Ib;

    2010-01-01

    Methane steam reforming is the key reaction to produce synthesis gas and hydrogen at the industrial scale. Here the kinetics of methane steam reforming over a rhodium-based catalyst is investigated in the temperature range 500-800 A degrees C and as a function of CH4, H2O and H-2 partial pressures...

  18. Discovery of Rubidium, Strontium, Molybdenum, and Rhodium Isotopes

    OpenAIRE

    Parker, A. M.; Thoennessen, M

    2011-01-01

    Currently, thirty-one rubidium, thirty-five strontium, thirty-five molybdenum and thirty-eight rhodium isotopes have been observed and the discovery of these isotopes is discussed here. For each isotope a brief synopsis of the first refereed publication, including the production and identification method, is presented.

  19. Intercalated compounds of niobium and tantalum dicalcogenides

    International Nuclear Information System (INIS)

    The synthesis of niobium and tantalum lamellar compounds and its intercalated derivatives is described. The intercalated compounds with lithium, with alkaline metal and with metals of the first-row transition are studied, characterized by X-ray diffraction. (C.G.C.)

  20. Intercalation chemistry of zirconium 4-sulfophenylphosphonate

    Energy Technology Data Exchange (ETDEWEB)

    Svoboda, Jan [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovský Sq. 2, 162 06 Prague 6 (Czech Republic); Zima, Vítězslav, E-mail: vitezslav.zima@upce.cz [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovský Sq. 2, 162 06 Prague 6 (Czech Republic); Melánová, Klára [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovský Sq. 2, 162 06 Prague 6 (Czech Republic); Beneš, Ludvík [Faculty of Chemical Technology, University of Pardubice, 532 10 Pardubice (Czech Republic); Trchová, Miroslava [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovský Sq. 2, 162 06 Prague 6 (Czech Republic)

    2013-12-15

    Zirconium 4-sulfophenylphosphonate is a layered material which can be employed as a host for the intercalation reactions with basic molecules. A wide range of organic compounds were chosen to represent intercalation ability of zirconium 4-sulfophenylphosphonate. These were a series of alkylamines from methylamine to dodecylamine, 1,4-phenylenediamine, p-toluidine, 1,8-diaminonaphthalene, 1-aminopyrene, imidazole, pyridine, 4,4′-bipyridine, poly(ethylene imine), and a series of amino acids from glycine to 6-aminocaproic acid. The prepared compounds were characterized by powder X-ray diffraction, thermogravimetry analysis and IR spectroscopy and probable arrangement of the guest molecules in the interlayer space of the host is proposed based on the interlayer distance of the prepared intercalates and amount of the intercalated guest molecules. - Graphical abstract: Nitrogen-containing organic compounds can be intercalated into the interlayer space of zirconium 4-sulfophenylphosphonate. - Highlights: • Zirconium 4-sulfophenylphosphonate was examined as a host material in intercalation chemistry. • A wide range of nitrogen-containing organic compounds were intercalated. • Possible arrangement of the intercalated species is described.

  1. Triplex glue by synthesizing conjugated flexible intercalators.

    Science.gov (United States)

    Pedersen, Erik B; Osman, Amany M A; Globisch, Daniel; Paramasivam, Manikandan; Cogoi, Susanna; Bomholt, Niels; Jørgensen, Per T; Xodo, Luigi E; Filichev, Vyacheslav V

    2008-01-01

    Bulge insertions of conjugated intercalators into the DNA triplex structure are found to give a dramatic contribution to the triplex stability. On the other hand insertions of conjugated intercalators are found to diminish quadruplex structures and in this way breaking down the self association of G-rich oligonucleotides under physiologically potassium ion conditions. A large number of intercalators are described here and they all result in dramatic increases of thermal stability of the corresponding triplexes. Another interesting aspect of conjugated intercalators is their use for assembling alternate strand triplexes. Targeting of neighbouring purine sequences on each their strand in the duplex DNA is a challenge for the 5'- 5' connectivity of the TFOs because of a large distance between the 5'-ends. The intercalator approach offers a linkage with the proper combination of flexibility and rigidity to produce alternate strand triplexes with higher stability than a similar wild type triplex of the same total length. PMID:18776241

  2. Modern induction chemotherapy before chemoradiation for bulky locally-advanced nonsmall cell lung cancer improves survival

    Directory of Open Access Journals (Sweden)

    Inaya Ahmed

    2016-01-01

    Conclusion: In patients with large tumors or bulky nodal NSCLC, carboplatin-based induction chemotherapy may be an important addition to definitive CCRT in the modern era. Our findings strongly support further investigation induction chemotherapy in this population.

  3. Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports.

    Science.gov (United States)

    Strayer, Megan E; Binz, Jason M; Tanase, Mihaela; Shahri, Seyed Mehdi Kamali; Sharma, Renu; Rioux, Robert M; Mallouk, Thomas E

    2014-04-16

    Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al0.02)O10.02F1.96), and α-Zr(HPO4)2·H2O. High surface area SiO2 and γ-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with ΔH values in the range -32 kJ·mol(-1) Rh to -37 kJ·mol(-1) Rh. In contrast, the interaction enthalpy was positive with SiO2 and γ-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and α-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports. PMID:24654835

  4. Osazone anion radical complex of rhodium(III).

    Science.gov (United States)

    Patra, Sarat Chandra; Biswas, Manas Kumar; Maity, Amarendra Nath; Ghosh, Prasanta

    2011-02-21

    One electron paramagnetic parent osazone complex of rhodium of type trans-Rh(L(NHPh)H(2))(PPh(3))(2)Cl(2) (1), defined as an osazone anion radical complex of rhodium(III), trans-Rh(III)(L(NHPh)H(2)(•-))(PPh(3))(2)Cl(2), 1((t-RhL•)), with a minor contribution (∼2%) of rhodium(II) electromer, trans-Rh(II)(L(NHPh)H(2))(PPh(3))(2)Cl(2), 1((t-Rh•L)), and their nonradical congener, trans-[Rh(III)(L(NHPh)H(2))(PPh(3))(2)Cl(2)]I(3) ([t-1](+)I(3)(-)), have been isolated and are substantiated by spectra, bond parameters, and DFT calculations on equivalent soft complexes [Rh(L(NHPh)H(2))(PMe(3))(2)Cl(2)] (3) and [Rh(L(NHPh)H(2))(PMe(3))(2)Cl(2)](+) (3(+)). 1 is not stable in solution and decomposes to [t-1](+) and a new rhodium(I) osazone complex, [Rh(I)(L(NHPh)H(2))(PPh(3))Cl] (2). 1 absorbs strongly at 351 nm due to MLCT and LLCT, while [t-1](+) and 2 absorb moderately in the range of 300-450 nm, respectively, due to LMCT and MLCT elucidated by TD-DFT calculations on 3((t-RhL•)), [t-3](+), and Rh(I)(L(NHPh)H(2))(PMe(3))Cl (4). EPR spectra of solids at 295 and 77 K, and dichloromethane-toluene frozen glass at 77 K of 1 are similar with g = 1.991, while g = 2.002 for the solid at 25 K. The EPR signal of 1 in dichloromethane solution is weaker (g = 1.992). In cyclic voltammetry, 1 displays two irreversible one electron transfer waves at +0.13 and -1.22 V, with respect to Fc(+)/Fc coupling, due to oxidation of 1((t-RhL•)) to [t-1](+) at the anode and reduction of rhodium(III) to rhodium(II), i.e., [t-1](+) to electromeric 1((t-Rh•L)) at the cathode. PMID:21261283

  5. Effect of water intercalation on VOx layers in dodecylamine-intercalated vanadium oxide nanotubes

    Science.gov (United States)

    Kweon, Hyocheon; Lee, Kyu Won; Lee, Eun Mo; Park, Jitae; Kim, I.-M.; Lee, Cheol Eui; Jung, G.; Gedanken, A.; Koltypin, Yu.

    2007-07-01

    Dodecylamine-intercalated vanadium oxide nanotubes were obtained by distinct synthesis processes. Water intercalation in the nanotube structure was identified in a marked manner by the distortion of the VOx layers in the x-ray diffraction patterns and enhanced V4+O absorption in the Fourier-transform infrared spectra. Our electron spin resonance measurements sensitively reflect changes in the microscopic structure and magnetic interactions introduced by the water intercalation in the vanadium oxide nanotubes.

  6. Plasmonics in the UV range with Rhodium nanocubes

    Science.gov (United States)

    Zhang, X.; Gutiérrez, Y.; Li, P.; Barreda, Á. I.; Watson, A. M.; Alcaraz de la Osa, R.; Finkelstein, G.; González, F.; Ortiz, D.; Saiz, J. M.; Sanz, J. M.; Everitt, H. O.; Liu, J.; Moreno, F.

    2016-04-01

    Plasmonics in the UV-range constitutes a new challenge due to the increasing demand to detect, identify and destroy biological toxins, enhance biological imaging, and characterize semiconductor devices at the nanometer scale. Silver and aluminum have an efficient plasmonic performance in the near UV region, but oxidation reduces its performance in this range. Recent studies point out rhodium as one of the most promising metals for this purpose: it has a good plasmonic response in the UV and, as gold in the visible, it presents a low tendency to oxidation. Moreover, its easy fabrication through chemical means and its potential for photocatalytic applications, makes this material very attractive for building plasmonic tools in the UV. In this work, we will show an overview of our recent collaborative research with rhodium nanocubes (NC) for Plasmonics in the UV.

  7. Surface science studies of Cobalt and Rhodium single crystal surfaces

    OpenAIRE

    Ramsvik, Trond

    2001-01-01

    The main topic of this thesis is the investigation of small molecules adsorbed on the transition metals cobalt and rhodium surfaces by means of predominantly high-resolution core level photoemission and near edge x-ray absorption fine structure (NEXAFS). The thesis can be divided into three parts where the following phenomena are examined:1) internal molecular vibrations in the core level photoemission spectra2) hybridisation and thermal decomposition of adsorbates3) growth and surface alloy ...

  8. Bioenvironmental aspects of europium and rhodium: a selected bibliography

    International Nuclear Information System (INIS)

    This bibliography of 428 abstracted references represents a summary of the domestic and foreign literature relevant to the biological and environmental aspects of europium and rhodium. The collected data are organized by current NAEG interests - research highlighting inventory and distribution of the radionulcides, ecological studies covering terrestrial and aquatic systems, and biological studies in both man and animals. Studies that focus directly on research conducted at specific sites (e.g., the Nevada Test Site) are emphasized throughout the bibliography

  9. Scalar Relativistic Study of the Structure of Rhodium Acetate

    Directory of Open Access Journals (Sweden)

    Emily E. Edwards

    2004-01-01

    Full Text Available Abstract: Rhodium acetate, related rhodium carboxylates, and rhodium amide complexes are powerful catalysts for carbene chemistry. They readily promote the decomposition of diazo compounds and transfer the resulting carbene to a variety of substrates. There have been several quantum chemistry studies of these compounds, particularly of the acetate. These have all used non-relativistic methods, and all have shown optimized Rh-Rh bond lengths significantly longer than the experimental value. In this study we have surveyed several scalar relativistic DFT methods using Gaussian, Slater, and numerical basis functions (in DGAUSS, ADF, and DMOL3. Several combinations of exchange-correlation functionals with relativistic and non-relativistic effective core potentials (ECP were investigated, as were non-relativistic and all electron scalar relativistic methods. The combination of the PW91 exchange and PW91 correlation functional with the Christiansen-Ermler ECP gave the best results: 2.3918 Å compared to the experimental value of 2.3855±0.0005 Å.

  10. Resistance to Nucleotide Excision Repair of Bulky Guanine Adducts Opposite Abasic Sites in DNA Duplexes and Relationships between Structure and Function.

    Directory of Open Access Journals (Sweden)

    Zhi Liu

    Full Text Available The nucleotide excision repair of certain bulky DNA lesions is abrogated in some specific non-canonical DNA base sequence contexts, while the removal of the same lesions by the nucleotide excision repair mechanism is efficient in duplexes in which all base pairs are complementary. Here we show that the nucleotide excision repair activity in human cell extracts is moderate-to-high in the case of two stereoisomeric DNA lesions derived from the pro-carcinogen benzo[a]pyrene (cis- and trans-B[a]P-N2-dG adducts in a normal DNA duplex. By contrast, the nucleotide excision repair activity is completely abrogated when the canonical cytosine base opposite the B[a]P-dG adducts is replaced by an abasic site in duplex DNA. However, base excision repair of the abasic site persists. In order to understand the structural origins of these striking phenomena, we used NMR and molecular spectroscopy techniques to evaluate the conformational features of 11mer DNA duplexes containing these B[a]P-dG lesions opposite abasic sites. Our results show that in these duplexes containing the clustered lesions, both B[a]P-dG adducts adopt base-displaced intercalated conformations, with the B[a]P aromatic rings intercalated into the DNA helix. To explain the persistence of base excision repair in the face of the opposed bulky B[a]P ring system, molecular modeling results suggest how the APE1 base excision repair endonuclease, that excises abasic lesions, can bind productively even with the trans-B[a]P-dG positioned opposite the abasic site. We hypothesize that the nucleotide excision repair resistance is fostered by local B[a]P residue-DNA base stacking interactions at the abasic sites, that are facilitated by the absence of the cytosine partner base in the complementary strand. More broadly, this study sets the stage for elucidating the interplay between base excision and nucleotide excision repair in processing different types of clustered DNA lesions that are substrates of

  11. Polymerization in Liquid Crystal Medium: Preparation of Polythiophene Derivatives Bearing a Bulky Pyrimidine Substituent

    Directory of Open Access Journals (Sweden)

    Hiromasa Goto

    2010-10-01

    Full Text Available We carried out polycondensation of monomers bearing a bulky pyrimidine substituent in a liquid crystal solvent. The resultant polymers formed nematic liquid crystals. The polymers prepared in liquid crystals had higher coplanarity than the polymers prepared in toluene. This can be due to the fact that the ordered medium of the liquid crystal produces an aggregated structure with well-developed π-stacking between the main chains. The present results demonstrated that polymerization of bulky monomers is possible in liquid crystal solvents.

  12. Hydrogen intercalation under graphene on Ir(111)

    Science.gov (United States)

    Grånäs, Elin; Gerber, Timm; Schröder, Ulrike A.; Schulte, Karina; Andersen, Jesper N.; Michely, Thomas; Knudsen, Jan

    2016-09-01

    Using high resolution X-ray photoelectron spectroscopy and scanning tunneling microscopy we study the intercalation of hydrogen under graphene/Ir(111). The hydrogen intercalated graphene is characterized by a component in C 1s that is shifted -0.10 to -0.18 eV with respect to pristine graphene and a component in Ir 4f at 60.54 eV. The position of this Ir 4f component is identical to that of the Ir(111) surface layer with hydrogen atoms adsorbed, indicating that the atomic hydrogen adsorption site on bare Ir(111) and beneath graphene is the same. Based on co-existence of fully- and non-intercalated graphene, and the inability to intercalate a closed graphene film covering the entire Ir(111) surface, we conclude that hydrogen dissociatively adsorbs at bare Ir(111) patches, and subsequently diffuses rapidly under graphene. A likely entry point for the intercalating hydrogen atoms is identified to be where graphene crosses an underlying Ir(111) step.

  13. Gas-phase chemistry of ruthenium and rhodium carbonyl complexes.

    Science.gov (United States)

    Cao, Shiwei; Wang, Yang; Qin, Zhi; Fan, Fangli; Haba, Hiromitsu; Komori, Yukiko; Wu, Xiaolei; Tan, Cunmin; Zhang, Xin

    2016-01-01

    Short-lived ruthenium and rhodium isotopes were produced from a (252)Cf spontaneous fission (SF) source. Their volatile carbonyl complexes were formed in gas-phase reactions in situ with the carbon-monoxide containing gas. A gas-jet system was employed to transport the volatile carbonyls from the recoil chamber to the chemical separation apparatus. The gas-phase chemical behaviors of these carbonyl complexes were studied using an online low temperature isothermal chromatography (IC) technique. Long IC columns made up of FEP Teflon were used to obtain the chemical information of the high-volatile Ru and Rh carbonyls. By excluding the influence of precursor effects, short-lived isotopes of (109-110)Ru and (111-112)Rh were used to represent the chemical behaviours of Ru and Rh carbonyls. Relative chemical yields of about 75% and 20% were measured for Ru(CO)5 and Rh(CO)4, respectively, relative to the yields of KCl aerosols transported in Ar gas. The adsorption enthalpies of ruthenium and rhodium carbonyl complexes on a Teflon surface were determined to be around ΔHads = -33(+1)(-2) kJ mol(-1) and -36(+2)(-1) kJ mol(-1), respectively, by fitting the breakthrough curves of the corresponding carbonyl complexes with a Monte Carlo simulation program. Different from Mo and Tc carbonyls, a small amount of oxygen gas was found to be not effective for the chemical yields of ruthenium and rhodium carbonyl complexes. The general chemical behaviors of short-lived carbonyl complexes of group VI-IX elements were discussed, which can be used in the future study on the gas-phase chemistry of superheavy elements - Bh, Hs, and Mt carbonyls. PMID:26573993

  14. Feasibility of intercalated graphite railgun armatures

    Science.gov (United States)

    Gaier, James R.; Gooden, Clarence E.; Yashan, Doreen; Naud, Steven

    1990-01-01

    Graphite intercalation compounds may provide an excellent material for the fabrication of electro-magnetic railgun armatures. As a pulse of power is fed into the armature the intercalate could be excited into the plasma state around the edges of the armature, while the bulk of the current would be carried through the graphite block. Such an armature would have the desirable characteristics of both diffuse plasma armatures and bulk conduction armatures. In addition, the highly anisotropic nature of these materials could enable the electrical and thermal conductivity to be tailored to meet the specific requirements of electromagnetic railgun armatures. Preliminary investigations were performed in an attempt to determine the feasibility of using graphite intercalation compounds as railgun armatures. Issues of fabrication, resistivity, stability, and electrical current spreading are addressed for the case of highly oriented pyrolytic graphite.

  15. The solubility of hydrogen in rhodium, ruthenium, iridium and nickel.

    Science.gov (United States)

    Mclellan, R. B.; Oates, W. A.

    1973-01-01

    The temperature variation of the solubility of hydrogen in rhodium, ruthenium, iridium, and nickel in equilibrium with H2 gas at 1 atm pressure has been measured by a technique involving saturating the solvent metal with hydrogen, quenching, and analyzing in resultant solid solutions. The solubilities determined are small (atom fraction of H is in the range from 0.0005 to 0.00001, and the results are consistent with the simple quasi-regular model for dilute interstitial solid solutions. The relative partial enthalpy and excess entropy of the dissolved hydrogen atoms have been calculated from the solubility data and compared with well-known correlations between these quantities.

  16. Photoinduced intercalation and coordination of a dirhodium complex to DNA: dual DNA binding.

    Science.gov (United States)

    Palmer, Alycia M; Burya, Scott J; Gallucci, Judith C; Turro, Claudia

    2014-06-01

    Two new complexes, cis-H,H-[Rh2 (OCCH3 NH)2 (LL)(CH3 CN)2 ](2+) , where LL=bpy (2, bpy=2,2'-bipyridine) and dppz (3, dppz=dipyrido[3,2-a:2',3'-c]phenazine), were prepared from the reaction of cis-H,H-[Rh2 (OCCH3 NH)2 (CH3 CN)6 ](2+) (1) with the corresponding bidentate ligand. The bpy and dppz ligands chelate to the same rhodium atom and are positioned trans to the amidato N atoms, as determined by the single crystal X-ray structure of 2. Irradiation of 2 and 3 with visible light in water results in the exchange of one CH3 CNeq ligand for an H2 O molecule with quantum yields, Φ400 , of 0.040 and 0.044, respectively (λirr =400 nm). The identities of the photoproducts of 2 and 3 were determined to be cis-H,H-[Rh2 (OCCH3 NH)2 (L)(H2 O)(CH3 CN)](2+) , where L is bpy (4) and dppz (5), respectively. Mobility shift assays show that 4 crosslinks double-stranded DNA, and ESI-MS experiments indicate that both 4 and 5 form covalent adducts with single-stranded DNA. In addition, relative viscosity and 2D NMR experiments show that the dppz ligand of 5 also intercalates into DNA upon irradiation, making 3 a dual-binding agent that both intercalates and covalently binds to DNA upon the absorption of visible light.

  17. Environmental, Dietary, Maternal, and Fetal Predictors of Bulky DNA Adducts in Cord Blood

    DEFF Research Database (Denmark)

    Pedersen, Marie; Mendez, Michelle A; Schoket, Bernadette;

    2015-01-01

    BACKGROUND: Bulky DNA adducts reflect genotoxic exposures, have been associated with lower birth weight, and may predict cancer risk. OBJECTIVE: We selected factors known or hypothesized to affect in utero adduct formation and repair and examined their associations with adduct levels in neonates....

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

    Science.gov (United States)

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

    2015-01-01

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

  19. Monitoring lipase-catalyzed interesterification for bulky fats modification with FT-IR/NIR spectroscopy

    DEFF Research Database (Denmark)

    Chang, Tinghong; Lai, Xuxin; Zhang, Hong;

    2005-01-01

    This work demonstrates the application of FT-IR and FT-NIR spectroscopy to monitor the enzymatic interesterification process for bulky fat modification. The reaction was conducted between palm stearin and coconut oil (70/30, w/w) with the catalysis of Lipozyme TL IM at 70°C in a batch reactor...

  20. Turning the Page: Forget about Those Bulky Backbreakers, Digital Textbooks Are the Future

    Science.gov (United States)

    Hill, Rebecca

    2010-01-01

    Remember when computers were mostly used in offices? They were big and bulky with about as much mobility as a beached whale. Forget about using them in the classroom. Forget about reading a book on them. Forget about an app, well, for anything. Today, computers are the number-one educational tool. In fact, no one can imagine a school without one.…

  1. Degradation of nonmodified and rhodium modified aluminide coating deposited on CMSX 4 superalloy.

    Science.gov (United States)

    Zagula-Yavorska, Maryana; Wierzbińska, Małgorzata; Gancarczyk, Kamil; Sieniawski, Jan

    2016-07-01

    The Ni-base superalloy CMSX 4 used in the turbine blades of aircraft engines was coated with rhodium layer (0.5-μm thick). Next coated CMSX 4 superalloy was aluminized by the CVD method. The rhodium modified aluminide coating and nonmodified aluminide coating were oxidized at 1100°C at the air atmosphere. The rhodium modified aluminide coating showed about twice better oxidation resistance than the nonmodified one. The spallation equal 62% of the total area was observed on the surface of the nonmodified coating whereas only 36% spallation area was observed on the surface of the rhodium modified aluminide coating after the oxidation test. The oxide layer formed on the surface of the nonmodified coating was composed of nonprotective (Ni,Cr)Al2 O4 and (Ni,Cr)O phases. Aluminium in the coating reacts with oxygen, forming a protective α-Al2 O3 oxide on the surface of the rhodium modified aluminide coating. When the oxide cracks and spalls due to oxidation, additional aluminium from the coating diffuses to the surface to form the oxide. The presence of protective Al2 O3 oxide on the surface of the rhodium modified aluminide coating slows coating degradation. Therefore, rhodium modified aluminide coating has better oxidation resistance than the nonmodified one.

  2. Modelling informally collected quantities of bulky waste and reusable items in Austria

    Energy Technology Data Exchange (ETDEWEB)

    Ramusch, R., E-mail: roland.ramusch@boku.ac.at; Pertl, A.; Scherhaufer, S.; Schmied, E.; Obersteiner, G.

    2015-10-15

    Highlights: • Informal collectors from Hungary collect bulky waste and reusable items in Austria. • Two methodologies were applied to estimate the informally collected quantities. • Both approaches lead to an estimation of roughly 100,000 t p.a. informally collected. • The formal Austrian system collects 72 kg/cap/yr of bulky waste, WEE & scrap metal. • Informal collection amounts to approx. 12 kg/cap/yr. - Abstract: Disparities in earnings between Western and Eastern European countries are the reason for a well-established informal sector actively involved in collection and transboundary shipment activities from Austria to Hungary. The preferred objects are reusable items and wastes within the categories bulky waste, WEEE and metals, intended to be sold on flea markets. Despite leading to a loss of recyclable resources for Austrian waste management, these informal activities may contribute to the extension of the lifetime of certain goods when they are reused in Hungary; nevertheless they are discussed rather controversially. The aim of this paper is to provide objective data on the quantities informally collected and transhipped. The unique activities of informal collectors required the development and implementation of a new set of methodologies. The concept of triangulation was used to verify results obtained by field visits, interviews and a traffic counting campaign. Both approaches lead to an estimation of approx. 100,000 t per year of reusable items informally collected in Austria. This means that in addition to the approx. 72 kg/cap/yr formally collected bulky waste, bulky waste wood, household scrap (excluding packaging) and WEEE, up to a further 12 kg/cap/yr might, in the case that informal collection is abandoned, end up as waste or in the second-hand sector.

  3. PHONONS IN GRAPHITE INTERCALATED WITH BROMINE

    OpenAIRE

    Batallan, F.; Rosenman, I.; Simon, C; Furdin, G.; Lauter, H.

    1981-01-01

    We have investigated the phonon spectrum in stage 2 graphite intercalate with bromine by using inelastic neutron scattering. We have observed longitudinal and transverse phonons along the c direction as well as in the layer plane. Results are presented for energies up to 15 THz at 300 K. A linear chain model explains most of our results.

  4. Mg intercalation into Ti2C building block

    Science.gov (United States)

    Yu, Xue-fang; Cheng, Jianbo; Liu, Zhenbo; Li, Qingzhong; Li, Wenzuo; Yang, Xin; Xiao, Bo

    2015-06-01

    Generally, intercalation occurs when foreign atoms intercalate into multi-layer structures, while adsorption occurs when foreign atoms interact with monolayer structures or surfaces. We performed an investigation on the Mg intercalation into Ti2C building block (MXene) from first-principles simulation. We found that Mg can favorably intercalate into MXene, forming the stable compound Ti2MgC, which corresponds to the stage I in the Li intercalation into graphite. Based on the evaluation of the average cell potential and the energy barrier of Mg diffusion for the most energetically stable structure, our results suggest that Ti2MgC is a potential anode for Mg ion batteries.

  5. SHORT-TIME ANALYSIS FOR ADJUVANT CHEMOTHERAPY IN PATIENTS WITH EARLY-STAGE BULKY CERVICAL CARCINOMA

    Institute of Scientific and Technical Information of China (English)

    令狐华; 徐小蓉; 梅耀宇; 唐均英; 唐良萏; 孙彤

    2003-01-01

    Objective: To investigate the effect of adjuvant chemotherapy on early stage cervical cancer with bulky tumor. Methods: Between Mar 1998 and Aug 2002, 162 patients of cervical cancer with Ib~IIa stage were investigated. 21 patients with bulky tumors (≥4cm) were managed by cisplatin-based chemotherapy followed by radical hysterectomy and pelvic lymphadenectomy (Bulky-chemo group, BC group). The change of tumor size, the depth of stromal invasion, lymph node metastasis and the involvement of surgical specimens were assessed after operation and compared with those in 57 patients with bulky tumors (Bulky-nonchemo group, BN group) and 84 patients with the tumor size less than 4cm (small group, S group) who underwent surgery as the first step of treatment. Chemotherapy with the same regimen was offered for another 1~2 cycles after operation and the survival situation was followed up. Results: The tumor size of 21 patients in BC group were decreased to varying degrees after chemotherapy, 15 patients were shown as clinical effectiveness (71.43%). And the blood loss during operation (352.35(19.01ml) was significantly lower than that in BN group (619.05(35.58ml), t=4.37) and that in S group (568.07(45.23ml, t=3.36) patients. The incidence of lymph node metastasis (9/78) in patients with bulky tumors was greatly higher than those with tumor size less than 4cm (3/84, X2=4.416); its prevalence rate of deep wall infiltration (8/78) was also higher than that of the latter group (2/84), while with no statistical significance (X2=3.089). Histology showed that there was no case of marginal involvement in all patients. The ratio of both deep stromal invasion (1/21) and positive lymph node (2/21) in BC group was lower than that in BN group (7/57, 7/57 respectively), but neither with statistical significance (X2=0.0103 and 0.8193 respectively). Conclusion: Pre-operative chemotherapy can improve decreasing the primary tumor size and facilitate the following radical surgery. While

  6. Improving the Quality of Thermocouple Wire Made of Platinum-rhodium Alloys

    Institute of Scientific and Technical Information of China (English)

    HORIKOV P.A.; MAMONOV S.N.; EFIMOV V.N.; RADKIN A.N.; DROZDOV D.E.

    2012-01-01

    For the manufacture of S-type thermocouple the so-called thermocouple wire of platinum and platinum-rhodium alloy is used.One of the main technical requirements for the quality of the wire,according to State Standard of Russia (GOST 10821),is the uniformity of its largest thermoelectric force (Thermo-emf) in the length different sections.It was found that a determining impact on the uniformity of the wire thermo-emf is the distribution of rhodium along the length of the wire.The impact of platinum- rhodium melt crystallization conditions on the inhomogeneity of wire manufactured from it.It was suggested that the chemical inhomogeneity of the wire is related to the liquation phase of platinum-rhodium alloy.

  7. Hydroaminomethylation of 1-Dodecene Catalyzed by Water-soluble Rhodium Complex

    Institute of Scientific and Technical Information of China (English)

    Ying Yong WANG; Mei Ming LUO; Yao Zhong LI; Hua CHEN; Xian Jun LI

    2004-01-01

    The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.

  8. Diversity synthesis using the complimentary reactivity of rhodium(II)- and palladium(II)-catalyzed reactions.

    Science.gov (United States)

    Ni, Aiwu; France, Jessica E; Davies, Huw M L

    2006-07-21

    Rhodium(II)-catalyzed reactions of aryldiazoacetates can be conducted in the presence of iodide, triflate, organoboron, and organostannane functionality, resulting in the formation of a variety of cyclopropanes or C-H insertion products with high stereoselectivity. The combination of the rhodium(II)-catalyzed reaction with a subsequent palladium(II)-catalyzed Suzuki coupling offers a novel strategy for diversity synthesis. PMID:16839138

  9. AlkB recognition of a bulky DNA base adduct stabilized by chemical cross-linking

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    E.coli AlkB is a direct DNA/RNA repair protein that oxidatively reverses N1 alkylated purines and N3 alkylated pyrimidines to regular bases.Previous crystal structures have revealed N1-methyl adenine(1-meA) recognition by AlkB and a unique base flipping mechanism,but how the AlkB active site can accommodate bulky base adducts is largely unknown.Employing a previously developed chemical cross-linking technique,we crystallized AlkB with a duplex DNA containing a caged thymine base(cagedT).The structure revealed a flexible hairpin lid and a reorganized substrate recognition loop used by AlkB to accommodate cagedT.These observations demonstrate,at the molecular level,how bulky DNA adducts may be recognized and processed by AlkB.

  10. Investigation of the Electrocatalytic Activity of Rhodium Sulfide for Hydrogen Evolution and Hydrogen Oxidation

    International Nuclear Information System (INIS)

    We report the synthesis of unsupported and carbon-supported, mixed phase, rhodium sulfide, using both a hydrogen sulfide source and a solid sulfur source. Samples with several different distributions of rhodium sulfide phases (Rh2S3, Rh17S15, RhS2 and metallic Rh) were obtained by varying the temperature and exposure time to H2S or sulfur to rhodium ratio when using solid sulfur. Samples were characterized by X-ray diffraction (XRD), and the unsupported rhodium sulfide compounds studied using Raman spectroscopy to link Raman spectra to catalyst phases. The electrocatalytic activity of the rhodium sulfide compounds for hydrogen evolution and oxidation was measured using rotating disk electrode measurements in acidic conditions to simulate use in a flow cell. The most active phases for hydrogen evolution were found to be Rh3S4 and Rh17S15 (−0.34 V vs. Ag/AgCl required for 20 mA/cm2), while Rh2S3 and RhS2 phases were relatively inactive (−0.46 V vs. Ag/AgCl required for 20 mA/cm2 using RhS2/C). The hydrogen oxidation activity of all rhodium sulfide phases is significantly lower than the hydrogen evolution activity and is not associated with conductivity limitations

  11. RESPONSE OF EARLY STAGE BULKY CERVICAL SQUAMOUS CARCINOMA TO PREOPERATIVE ADJUVANT CHEMOTHERAPY

    Institute of Scientific and Technical Information of China (English)

    Hua Linghu; Xiao-rong Xu; Yao-yu Mei; Jun-ying Tang; Liang-dan Tang; Tong Sun

    2004-01-01

    Objective To investigate the potential role of preoperative adjuvant chemotherapy on early stage cervical squamouscarcinoma with bulky tumor.Methods One hundred and forty-five patients with cervical squamous cancer stages Ⅰb-Ⅱa were investigated, among which 17 patients with bulky tumors (≥4 cm) were managed by cisplatin-based chemotherapy for 1-2 courses followed by radical hysterectomy and pelvic lymphadenectomy (BC group). The change of tumor size, pelvic lymph nodes metastasis, cervical wall invasion, the involvement of surgical specimen margin, and the blood loss during operation were assessed after operation and compared with those in 51 patients with bulky tumors (BN group) and 77 patients with small local tumors (S group)who underwent surgery directly.Results (1) The tumor size of 17 patients in BC group were decreased in various degrees after chemotherapy, with 13 patients of clinical effectiveness (76.47%). And the responsiveness pertained to neither histological differentiation nor size of local tumors. (2) Post-operative histology has showed that patients in BC and BN group have higher incidence of lymph node metastasis and deep cervical infiltration (5/68 and 3/68, respectively) than in S group (1/77 and 1/77, respectively) while with no statistical significance. (3) Blood loss during operation in BC group was less than BN and S group. (4) Seventeen patients, including those underwent surgeries of vaginal prolongation and/or ovarian transposition, appeared disease-free survival within the follow-up time.Conclusions Most of patients with bulky early stage cervical squamous carcinoma are sensitive to cisplatin-based chemotherapy, which could greatly reduce local tumor size and in turn facilitate the following operation by well controlling blood loss.

  12. Maternal diet and dioxin-like activity, bulky DNA adducts and micronuclei in mother-newborns

    Energy Technology Data Exchange (ETDEWEB)

    Pedersen, Marie, E-mail: mpedersen@creal.cat [Section of Environmental Health, Department of Public Health, University of Copenhagen, CSS, Oester Farimagsgade, Copenhagen K (Denmark); Halldorsson, Thorhallur I., E-mail: lur@ssi.dk [Faculty of Food Science and Nutrition, School of Health Sciences, University of Iceland Reykjavik (Iceland); Center for Fetal Programming, Department of Epidemiology, Statens Serum Institute, Copenhagen (Denmark); Autrup, Herman, E-mail: ha@mil.au.dk [School of Public Health, Department of Environmental and Occupational Medicine, Aarhus University, Aarhus (Denmark); Brouwer, Abraham, E-mail: Bram.Brouwer@bds.nl [BioDetection Systems B.V., Amsterdam (Netherlands); Besselink, Harrie, E-mail: Harrie.Besselink@bds.nl [BioDetection Systems B.V., Amsterdam (Netherlands); Loft, Steffen, E-mail: stl@sund.ku.dk [Section of Environmental Health, Department of Public Health, University of Copenhagen, CSS, Oester Farimagsgade, Copenhagen K (Denmark); Knudsen, Lisbeth E., E-mail: liek@sund.ku.dk [Section of Environmental Health, Department of Public Health, University of Copenhagen, CSS, Oester Farimagsgade, Copenhagen K (Denmark)

    2012-06-01

    Maternal diet can contribute to carcinogenic exposures and also modify effects of environmental exposures on maternal and fetal genetic stability. In this study, associations between maternal diet and the levels of dioxin-like plasma activity, bulky DNA adducts in white blood cells and micronuclei (MN) in lymphocytes from mother to newborns were examined. From 98 pregnant women living in the greater area of Copenhagen, Denmark in 2006-2007, maternal peripheral blood and umbilical cord blood were collected, together with information on health, environmental exposure and lifestyle. Maternal diet was estimated on the basis of maternal food frequency questionnaire (FFQ) completed by the end of pregnancy. Biomarkers were detected in paired blood samples through the dioxin-responsive chemical-activated luciferase expression (CALUX){sup Registered-Sign} bioassay, {sup 32}P-postlabelling technique and cytokinesis-block MN assay. Maternal preference for meats with dark surface were significantly associated with higher bulky DNA adducts in both maternal ({beta} 95%CI; 0.46 (0.08, 0.84)) and cord blood ({beta} 95%CI; 0.46 (0.05, 0.86)) before and after adjustment for potential confounders. No other significant associations between the 18 dietary variables and the biomarkers measured in maternal and fetal samples were identified. The present study suggests that maternal intake of meats with dark surface contributes to the bulky DNA adduct levels in maternal and umbilical cord blood. Relationship between food preparation and bulky DNA adducts appear to be captured by a FFQ while potential associations for other biomarkers might be more complex or need larger sample size.

  13. Maternal diet and dioxin-like activity, bulky DNA adducts and micronuclei in mother–newborns

    International Nuclear Information System (INIS)

    Maternal diet can contribute to carcinogenic exposures and also modify effects of environmental exposures on maternal and fetal genetic stability. In this study, associations between maternal diet and the levels of dioxin-like plasma activity, bulky DNA adducts in white blood cells and micronuclei (MN) in lymphocytes from mother to newborns were examined. From 98 pregnant women living in the greater area of Copenhagen, Denmark in 2006–2007, maternal peripheral blood and umbilical cord blood were collected, together with information on health, environmental exposure and lifestyle. Maternal diet was estimated on the basis of maternal food frequency questionnaire (FFQ) completed by the end of pregnancy. Biomarkers were detected in paired blood samples through the dioxin-responsive chemical-activated luciferase expression (CALUX)® bioassay, 32P-postlabelling technique and cytokinesis-block MN assay. Maternal preference for meats with dark surface were significantly associated with higher bulky DNA adducts in both maternal (β 95%CI; 0.46 (0.08, 0.84)) and cord blood (β 95%CI; 0.46 (0.05, 0.86)) before and after adjustment for potential confounders. No other significant associations between the 18 dietary variables and the biomarkers measured in maternal and fetal samples were identified. The present study suggests that maternal intake of meats with dark surface contributes to the bulky DNA adduct levels in maternal and umbilical cord blood. Relationship between food preparation and bulky DNA adducts appear to be captured by a FFQ while potential associations for other biomarkers might be more complex or need larger sample size.

  14. Bulky abdominal masses in pediatrics: iconographic essay; Massas abdominais volumosas em pediatria: ensaio iconografico

    Energy Technology Data Exchange (ETDEWEB)

    Reis, Fabiano; Faria, Andreia V.; Kluge, Patricia D.; Volpato, Ricardo G.; Santos, Sergio L.M. dos; Caserta, Nelson M.G. [Universidade Estadual de Campinas, SP (Brazil). Faculdade de Ciencias Medicas]. E-mail: fabiano97@bol.com.br

    2005-04-15

    The ultrasound, computerized tomography and magnetic resonance findings of 19 patients with abdominal bulky masses diagnosed as hydronephrosis, Wilms' tumor, neuroblastoma, adrenal carcinoma, sarcoma, hemangioendothelioma, hepatoblastoma, mesenchymal hamartoma, hepatocellular carcinoma, choledochal cyst, splenic cyst, lymphoma, enteric cyst, teratoma, hydrometrocolpos and lipoma are presented. Imaging findings (including ultrasound, computerized tomography and magnetic resonance imaging) are important tools for the evaluation of abdominal masses in pediatric patients and can contribute to the diagnosis and evaluation of the extension of these diseases. (author)

  15. Modelling informally collected quantities of bulky waste and reusable items in Austria.

    Science.gov (United States)

    Ramusch, R; Pertl, A; Scherhaufer, S; Schmied, E; Obersteiner, G

    2015-10-01

    Disparities in earnings between Western and Eastern European countries are the reason for a well-established informal sector actively involved in collection and transboundary shipment activities from Austria to Hungary. The preferred objects are reusable items and wastes within the categories bulky waste, WEEE and metals, intended to be sold on flea markets. Despite leading to a loss of recyclable resources for Austrian waste management, these informal activities may contribute to the extension of the lifetime of certain goods when they are reused in Hungary; nevertheless they are discussed rather controversially. The aim of this paper is to provide objective data on the quantities informally collected and transhipped. The unique activities of informal collectors required the development and implementation of a new set of methodologies. The concept of triangulation was used to verify results obtained by field visits, interviews and a traffic counting campaign. Both approaches lead to an estimation of approx. 100,000 t per year of reusable items informally collected in Austria. This means that in addition to the approx. 72 kg/cap/yr formally collected bulky waste, bulky waste wood, household scrap (excluding packaging) and WEEE, up to a further 12 kg/cap/yr might, in the case that informal collection is abandoned, end up as waste or in the second-hand sector. PMID:26209344

  16. Modelling informally collected quantities of bulky waste and reusable items in Austria.

    Science.gov (United States)

    Ramusch, R; Pertl, A; Scherhaufer, S; Schmied, E; Obersteiner, G

    2015-10-01

    Disparities in earnings between Western and Eastern European countries are the reason for a well-established informal sector actively involved in collection and transboundary shipment activities from Austria to Hungary. The preferred objects are reusable items and wastes within the categories bulky waste, WEEE and metals, intended to be sold on flea markets. Despite leading to a loss of recyclable resources for Austrian waste management, these informal activities may contribute to the extension of the lifetime of certain goods when they are reused in Hungary; nevertheless they are discussed rather controversially. The aim of this paper is to provide objective data on the quantities informally collected and transhipped. The unique activities of informal collectors required the development and implementation of a new set of methodologies. The concept of triangulation was used to verify results obtained by field visits, interviews and a traffic counting campaign. Both approaches lead to an estimation of approx. 100,000 t per year of reusable items informally collected in Austria. This means that in addition to the approx. 72 kg/cap/yr formally collected bulky waste, bulky waste wood, household scrap (excluding packaging) and WEEE, up to a further 12 kg/cap/yr might, in the case that informal collection is abandoned, end up as waste or in the second-hand sector.

  17. EMI Shields made from intercalated graphite composites

    Science.gov (United States)

    Gaier, James R.; Terry, Jennifer

    1995-01-01

    Electromagnetic interference (EMI) shielding typically makes up about twenty percent of the mass of a spacecraft power system. Graphite fiber/polymer composites have significantly lower densities and higher strengths than aluminum, the present material of choice for EMI shields, but they lack the electrical conductivity that enables acceptable shielding effectiveness. Bromine intercalated pitch-based graphite/epoxy composites have conductivities fifty times higher than conventional structural graphite fibers. Calculations are presented which indicate that EMI shields made from such composites can have sufficient shielding at less than 20% of the mass of conventional aluminum shields. EMI shields provide many functions other than EMI shielding including physical protection, thermal management, and shielding from ionizing radiation. Intercalated graphite composites perform well in these areas also. Mechanically, they have much higher specific strength and modulus than aluminum. They also have shorter half thicknesses for x-rays and gamma radiation than aluminum. Thermally, they distribute infra-red radiation by absorbing and re-radiating it rather than concentrating it by reflection as aluminum does. The prospects for intercalated graphite fiber/polymer composites for EMI shielding are encouraging.

  18. Superconducting graphite intercalation compounds with calcium

    Science.gov (United States)

    Emery, N.; Hérold, C.; Marêché, J.-F.; Lagrange, P.; Bellouard, C.; Lamura, G.; Di Gennaro, E.; Andreone, A.

    2008-04-01

    In the graphite-lithium-calcium system, four well-defined intercalation compounds were synthesised. Two of them, CaC 6 and Li 3Ca 2C 6, exhibit superconducting properties at 11.5 K and 11.15 K, respectively, the highest critical temperatures among those of graphite intercalation compounds. The samples are synthesised using a liquid-solid method allowing the preparation of pure bulk samples, auspicious for crystallographic and magnetic measurements. The crystal structure of CaC 6 was entirely specified; this compound crystallises in the R-3 m space group. The two-dimensional unit cell of Li 3Ca 2C 6 is hexagonal and commensurate with that of graphite and the intercalated sheets, very rich in metal, are seven-layered. The magnetic properties of these phases were studied with an applied field parallel and perpendicular to the graphene sheets. In both cases the magnetic phase diagram indicates that these compounds are type II superconducting materials slightly anisotropic in spite of their lamellar structure. In the case of CaC 6, in-plane magnetic penetration depth measurements show a clear exponential behaviour at low temperatures, consistent with an s-wave symmetry of the gap function, well fitted by the standard BCS theory in the dirty limit.

  19. De-intercalation process from Stage-1 to Stage-2 graphite intercalation compounds revisited

    Energy Technology Data Exchange (ETDEWEB)

    Chacon-Torres, J.C.; Pichler, T. [Faculty of Physics, University of Vienna, Strudlhofgasse 4, 1090 Vienna (Austria); Ganin, A.Y.; Rosseinsky, M.J. [Department of Chemistry, University of Liverpool, Liverpool L69 7ZD (United Kingdom)

    2012-12-15

    The identification and contribution of the different phonons present in the G-line Raman response in Stage-1 and Stage-2 graphite intercalation compounds (GIC) is crucial for a correct stage determination. Different factors like laser induced de-intercalation play an important role in the precise stage assignment of these phases, and their intrinsic Raman response. In this contribution, an in situ micro-Raman analysis was conducted under high-vacuum conditions. Local heating of the samples was induced by using a high laser power (8.5 mW) in order to study the de-intercalation process from Stage-1 to Stage-2 GICs. A detailed Raman line-shape analysis was performed from the recorded spectra to determine the changes from the G-line response of KC{sub 8}, CaC{sub 6}, and LiC{sub 6}. We confirmed the assignment of the broad E{sub 2g} Fano mode at {proportional_to}1510 cm{sup -1} to the intrinsic Stage-1 Raman response in GICs. Additionally, the most evident change from Stage-1 to Stage-2 was observed in an asymmetric Fano mode in the range of 1565-1610 cm{sup -1}. This mode is linked to the first-order stretching Raman mode of Graphite, which tends to increase in frequency and decrease in width as function of de-intercalation. Finally, the response of the Stage-2 phase after de-intercalation was confirmed to be a useful benchmark for the identification of the intercalation stage in highly doped GICs. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Charge carrier density in Li-intercalated graphene

    KAUST Repository

    Kaloni, Thaneshwor P.

    2012-05-01

    The electronic structures of bulk C 6Li, Li-intercalated free-standing bilayer graphene, and Li-intercalated bilayer and trilayer graphene on SiC(0 0 0 1) are studied using density functional theory. Our estimate of Young\\'s modulus suggests that Li-intercalation increases the intrinsic stiffness. For decreasing Li-C interaction, the Dirac point shifts to the Fermi level and the associated band splitting vanishes. For Li-intercalated bilayer graphene on SiC(0 0 0 1) the splitting at the Dirac point is tiny. It is also very small at the two Dirac points of Li-intercalated trilayer graphene on SiC(0 0 0 1). For all the systems under study, a large enhancement of the charge carrier density is achieved by Li intercalation. © 2012 Elsevier B.V. All rights reserved.

  1. An improved Mesri creep model for unsaturated weak intercalated soils

    Institute of Scientific and Technical Information of China (English)

    祝艳波; 余宏明

    2014-01-01

    The weak intercalated soils in redbed soft rocks of Badong formation have obvious creep characters. In order to predict the unsaturated creep behaviors of weak intercalated soils, an unsaturated creep model was established based on the unsaturated creep tests of weak intercalated soils by using GDS triaxial apparatus. The results show that the creep behaviors of intercalated soils are apparent and significantly affected by matric suction. Based on this, an empirical Mesri creep model for intercalated soils under varying matric suctions was built. The fitting results show that the parameters Ed and m of this model are in good power relations with matric suction s and stress level Dr, respectively. An improved Mesri creep model was established involving stress−matric suction−strain−time, which is more precise than the Mesri creep model in predicting the unsaturated creep behaviors of weak intercalated soils.

  2. The intercalation chemistry of layered iron chalcogenide superconductors

    Science.gov (United States)

    Vivanco, Hector K.; Rodriguez, Efrain E.

    2016-10-01

    The iron chalcogenides FeSe and FeS are superconductors composed of two-dimensional sheets held together by van der Waals interactions, which makes them prime candidates for the intercalation of various guest species. We review the intercalation chemistry of FeSe and FeS superconductors and discuss their synthesis, structure, and physical properties. Before we review the latest work in this area, we provide a brief background on the intercalation chemistry of other inorganic materials that exhibit enhanced superconducting properties upon intercalation, which include the transition metal dichalcogenides, fullerenes, and layered cobalt oxides. From past studies of these intercalated superconductors, we discuss the role of the intercalates in terms of charge doping, structural distortions, and Fermi surface reconstruction. We also briefly review the physical and chemical properties of the host materials-mackinawite-type FeS and β-FeSe. The three types of intercalates for the iron chalcogenides can be placed in three categories: 1.) alkali and alkaline earth cations intercalated through the liquid ammonia technique; 2.) cations intercalated with organic amines such as ethylenediamine; and 3.) layered hydroxides intercalated during hydrothermal conditions. A recurring theme in these studies is the role of the intercalated guest in electron doping the chalcogenide host and in enhancing the two-dimensionality of the electronic structure by spacing the FeSe layers apart. We end this review discussing possible new avenues in the intercalation chemistry of transition metal monochalcogenides, and the promise of these materials as a unique set of new inorganic two-dimensional systems.

  3. Superconductivity of TiNCl intercalated with diamines

    Energy Technology Data Exchange (ETDEWEB)

    Yamanaka, Shoji, E-mail: syamana@hiroshima-u.ac.j [Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527 (Japan); Umemoto, Keita [Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527 (Japan)

    2010-12-15

    Intercalation compounds of TiNCl with ethylenediamine (EDA) and hexamethylenediamine (HDA) were prepared. The basal spacing of TiNCl increased by 3.3-3.9 A upon intercalation, implying that the molecules are lying with the alkyl chains parallel to the TiNCl layers in both compounds. The intercalated compounds showed superconductivity with transition temperatures (T{sub c}s) of 10.5 and 15.5 K for EDA and HDA, respectively, which are higher than 8.6 K of pyridine (Py) intercalated compound, Py{sub 0.25}TiNCl.

  4. Rhodium mediated bond activation: from synthesis to catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Ho, Hung-An [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    Recently, our lab has developed monoanionic tridentate ligand, ToR, showing the corresponding coordination chemistry and catalyst reactivity of magnesium, zirconium, zinc and iridium complexes. This thesis details synthetic chemistry, structural study and catalytic reactivity of the ToR-supported rhodium compounds. Tl[ToR] has been proved to be a superior ligand transfer agent for synthesizing rhodium complexes. The salt metathesis route of Tl[ToM] with [Rh(μ-Cl)(CO)]2 and [Rh(μ- Cl)(COE)]2 gives ToMRh(CO)2 (2.2) and ToMRhH(β3-C8H13) (3.1) respectively while Tl[ToM] with [Rh(μ-Cl)(CO)]2 affords ToPRh(CO)2 (2.3). 2.2 reacts with both strong and weak electrophiles, resulting in the oxazoline N-attacked and the metal center-attacked compounds correspondingly. Using one of the metal center-attacked electrophiles, 2.3 was demonstrated to give high diastereoselectivity. Parallel to COE allylic C-H activation complex 3.1, the propene and allylbenzene allylic C-H activation products have also been synthesized. The subsequent functionalization attempts have been examined by treating with Brønsted acids, Lewis acids, electrophiles, nucleophiles, 1,3-dipolar reagents and reagents containing multiple bonds able to be inserted. Various related complexes have been obtained under these conditions, in which one of the azide insertion compounds reductively eliminates to give an allylic functionalization product stoichiometrically. 3.1 reacts with various primary alcohols to give the decarbonylation dihydride complex ToMRh(H)2CO (4.1). 4.1 shows catalytic reactivity for primary alcohol decarbonylation under a photolytic condition. Meanwhile, 2.2 has been found to be more reactive than 4.1 for catalytic alcohol decarbonylation under the same condition. Various complexes and primary

  5. Branching Out: Rhodium-Catalyzed Allylation with Alkynes and Allenes.

    Science.gov (United States)

    Koschker, Philipp; Breit, Bernhard

    2016-08-16

    We present a new and efficient strategy for the atom-economic transformation of both alkynes and allenes to allylic functionalized structures via a Rh-catalyzed isomerization/addition reaction which has been developed in our working group. Our methodology thus grants access to an important structural class valued in modern organic chemistry for both its versatility for further functionalization and the potential for asymmetric synthesis with the construction of a new stereogenic center. This new methodology, inspired by mechanistic investigations by Werner in the late 1980s and based on preliminary work by Yamamoto and Trost, offers an attractive alternative to other established methods for allylic functionalization such as allylic substitution or allylic oxidation. The main advantage of our methodology consists of the inherent atom economy in comparison to allylic oxidation or substitution, which both produce stoichiometric amounts of waste and, in case of the substitution reaction, require prefunctionalization of the starting material. Starting out with the discovery of a highly branched-selective coupling reaction of carboxylic acids with terminal alkynes using a Rh(I)/DPEphos complex as the catalyst system, over the past 5 years we were able to continuously expand upon this chemistry, introducing various (pro)nucleophiles for the selective C-O, C-S, C-N, and C-C functionalization of both alkynes and the double-bond isomeric allenes by choosing the appropriate rhodium/bidentate phosphine catalyst. Thus, valuable compounds such as branched allylic ethers, sulfones, amines, or γ,δ-unsaturated ketones were successfully synthesized in high yields and with a broad substrate scope. Beyond the branched selectivity inherent to rhodium, many of the presented methodologies display additional degrees of selectivity in regard to regio-, diastereo-, and enantioselective transformations, with one example even proceeding via a dynamic kinetic resolution. Many advances

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

    International Nuclear Information System (INIS)

    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 CO32− solutions imply that Mg3Al–VC LDH is a better controlled release system than Mg3Fe–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 CO32− solution. - Graphical abstract: Vitamin C anions have been intercalated in the interlayer space of layered double hydroxide and released in CO32− 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 CO32− 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 CO32− solution

  7. Initial Stages in the Rhodium(III)-Catalyzed C-H Bond Activation of Primary Alcohols in Aqueous Solution

    DEFF Research Database (Denmark)

    Eriksen, J.; Monsted, L.; Monsted, O.;

    2010-01-01

    The mechanism of the catalytic HID exchange in primary alcohol substrates derived from aldopentoses, promoted by a macrocyclic rhodium(III) complex, has been shown to occur by a reversible redox reaction that gives aldehyde and a rhodium hydride complex. Hydride exchange in the latter complex pro...

  8. Hydroformylation of methyl oleate catalyzed by rhodium complexes; Hidroformilacao do oleato de metila catalisada por complexos de rodio

    Energy Technology Data Exchange (ETDEWEB)

    Mendes, Ana Nery Furlan [Universidade Federal do Espirito Santo (UFES), Sao Mateus, ES (Brazil). Centro Universitario Norte do Espirito Santo. Dept. de Ciencias Naturais; Rosa, Ricardo Gomes da; Gregorio, Jose Ribeiro, E-mail: jrg@iq.ufrgs.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica

    2012-07-01

    In this work, we describe the hydroformylation of methyl oleate catalyzed by several rhodium complexes. Parameters including total pressure, phosphorous/rhodium and CO/H{sub 2} ratio, temperature and phosphorous ligands were scanned. Total conversion of the starting double bonds was achieved while maintaining excellent selectivity in aldehydes. (author)

  9. Dosimetric study in ocular brachytherapy with iodine 125 and ruthenium/rhodium-106

    International Nuclear Information System (INIS)

    To analyze dose distribution utilizing plaques with iodine-125 and ruthenium/rhodium-106 in a computational model of the ocular region. A voxel-based computational model including the different tissues of the ocular region was utilized with the plaque positioned on the sclera. The Monte Carlo code was utilized for simulating irradiation. The dose distribution is demonstrated by isodoses curves. Computational simulations demonstrate the dose distribution inside the ocular bulb as well as in adjacent outside structures. The results have allowed the authors to compare the spatial distribution of doses generated by beta particles and photons. The simulations demonstrated that the utilization of iodine-125 seeds implies a high dose to the crystalline lens, while ruthenium/rhodium-106 results in high dose on the sclera surface. The dose to the crystalline lens depends on the tumor position and thickness, the plaque diameter, and the radionuclide utilized. In the present study, the ruthenium/rhodium-106 source is recommended for low tumor thickness. Irradiation with iodine-125 results in higher doses to the crystalline lens than irradiation with ruthenium/rhodium-106. The maximum value for dose to the crystalline lens corresponds to 12.75% of the maximum dose with iodine-125 and only 0.005% for ruthenium/rhodium-106. (author)

  10. In situ dynamic study of hydrogen oxidation on rhodium.

    Science.gov (United States)

    Visart de Bacarmé, T; Bär, T; Kruse, N

    2001-10-01

    The reaction of hydrogen/oxygen gas mixtures with rhodium single crystals was studied using video-FIM (Field Ion Microscopy) at temperatures between 350 and 550 K and up to 2 x 10(-2) Pa total pressure. Imaging at 500 K in a hydrogen rich gas mixture (H2:O2 = 9) revealed considerable morphological changes of the (0 0 1)-oriented field emitter tip, i.e. the growth of low-index at the expense of high-index planes and strong crystal coarsening. Decreasing the hydrogen partial pressure led to chemical and structural changes of the Rh sample. Starting on the [1 1 0] planes a surface oxide formed, which spread anisotropically across the surface until it finally covered the whole visible surface area. The transformation was reversible upon increasing the hydrogen pressure back to its initial value. However, a hysteresis behavior was observed, i.e. a larger hydrogen partial pressure was found to be necessary to re-establish the initial patterns of a reactive Oad/Had layer. By varying the temperature from 400 to 500 K a phase diagram was established for the Oad/Had system. Increasing the electric field proved to shift the phase diagram towards higher H2 pressures. At 550K self-sustained kinetic oscillations with a cycle time of approximately 40s could be observed. PMID:11770755

  11. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grass, Michael Edward [Univ. of California, Berkeley, CA (United States)

    2008-09-01

    Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

  12. Superconductivity in alkali metal intercalated iron selenides

    Science.gov (United States)

    Krzton-Maziopa, A.; Svitlyk, V.; Pomjakushina, E.; Puzniak, R.; Conder, K.

    2016-07-01

    Alkali metal intercalated iron selenide superconductors A x Fe2‑y Se2 (where A  =  K, Rb, Cs, Tl/K, and Tl/Rb) are characterized by several unique properties, which were not revealed in other superconducting materials. The compounds crystallize in overall simple layered structure with FeSe layers intercalated with alkali metal. The structure turned out to be pretty complex as the existing Fe-vacancies order below ~550 K, which further leads to an antiferromagnetic ordering with Néel temperature fairly above room temperature. At even lower temperatures a phase separation is observed. While one of these phases stays magnetic down to the lowest temperatures the second is becoming superconducting below ~30 K. All these effects give rise to complex relationships between the structure, magnetism and superconductivity. In particular the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, is assumed to be an intrinsic property of the system. Since the discovery of superconductivity in those compounds in 2010 they were investigated very extensively. Results of the studies conducted using a variety of experimental techniques and performed during the last five years were published in hundreds of reports. The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations.

  13. Benzenesulfonamides incorporating bulky aromatic/heterocyclic tails with potent carbonic anhydrase inhibitory activity.

    Science.gov (United States)

    Bozdag, Murat; Alafeefy, Ahmed M; Vullo, Daniela; Carta, Fabrizio; Dedeoglu, Nurcan; Al-Tamimi, Abdul-Malek S; Al-Jaber, Nabila A; Scozzafava, Andrea; Supuran, Claudiu T

    2015-12-15

    Three series of sulfonamides incorporating long, bulky tails were obtained by applying synthetic strategies in which substituted anthranilic acids, quinazolines and aromatic sulfonamides have been used as starting materials. They incorporate long, bulky diamide-, 4-oxoquinazoline-3-yl- or quinazoline-4-yl moieties in their molecules, and were investigated for the inhibition of four physiologically relevant carbonic anhydrase (CA, EC 4.2.1.1) isoforms, the cytosolic human (h) hCA I and II, as well as the transmembrane hCA IX and XII. Most of the new sulfonamides showed excellent inhibitory effects against the four isoforms, with KIs of 7.6-322nM against hCA I, of 0.06-85.4nM against hCA II; of 6.7-152nM against hCA IX and of 0.49-237nM against hCA XII; respectively. However no relevant isoform-selective behavior has been observed for any of them, although hCA II and XII, isoforms involved in glaucoma-genesis were the most inhibited ones. The structure-activity relationship for inhibiting the four CAs with these derivatives is discussed in detail. PMID:26639945

  14. Bulky Macroporous TiO2 Photocatalyst with Cellular Structure via Facile Wood-Template Method

    Directory of Open Access Journals (Sweden)

    Qingfeng Sun

    2013-01-01

    Full Text Available We report a bulky macroporous TiO2 particles with cellular structure prepared in the presence of wood slices as template. Firstly, TiO2 sol was coated onto the wood slices by repeated dip-coating process. Then, after calcinations at 550°C, the wood template could be removed, and the bulky TiO2 structure was obtained. The prepared samples were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD, energy dispersive spectroscopy (EDS, and transmission electron microscope (TEM techniques. XRD pattern confirmed the crystalline phase of the wood-templated TiO2 is anatase phase. And interestingly, from the observation of SEM image, the wood-templated TiO2 inherited the initial cellular structures of birch lumber (B. albosinensis Burk, and numerous macropores were observed in the sample. Meanwhile, the wood-templated TiO2 presented a superior photocatalytic ability to decompose Rhodamine B (RhB under ultraviolet irradiation.

  15. Quasi-freestanding graphene on Ni(111) by Cs intercalation

    Science.gov (United States)

    Alattas, M.; Schwingenschlögl, U.

    2016-05-01

    A possible approach to achieve quasi-freestanding graphene on a substrate for technological purpose is the intercalation of alkali metal atoms. Cs intercalation between graphene and Ni(111) therefore is investigated using density functional theory, incorporating van der Waals corrections. It is known that direct contact between graphene and Ni(111) perturbs the Dirac states. We find that Cs intercalation restores the linear dispersion characteristic of Dirac fermions, which agrees with experiments, but the Dirac cone is shifted to lower energy, i.e., the graphene sheet is n-doped. Cs intercalation therefore decouples the graphene sheet from the substrate except for a charge transfer. On the other hand, the spin polarization of Ni(111) does not extend through the intercalated atoms to the graphene sheet, for which we find virtually spin-degeneracy.

  16. Quasi-freestanding graphene on Ni(111) by Cs intercalation

    KAUST Repository

    Alattas, M.

    2016-05-26

    A possible approach to achieve quasi-freestanding graphene on a substrate for technological purpose is the intercalation of alkali metal atoms. Cs intercalation between graphene and Ni(111) therefore is investigated using density functional theory, incorporating van der Waals corrections. It is known that direct contact between graphene and Ni(111) perturbs the Dirac states. We find that Cs intercalation restores the linear dispersion characteristic of Dirac fermions, which agrees with experiments, but the Dirac cone is shifted to lower energy, i.e., the graphene sheet is n-doped. Cs intercalation therefore decouples the graphene sheet from the substrate except for a charge transfer. On the other hand, the spin polarization of Ni(111) does not extend through the intercalated atoms to the graphene sheet, for which we find virtually spin-degeneracy.

  17. New Conditions for Intercalation of Organic Compounds into Semiconductor Nanomaterial

    Institute of Scientific and Technical Information of China (English)

    A.A.El-Meligi

    2009-01-01

    The intercalation of organic guests, 2-methyl pyridine (2-picoline) and 3-methyl pyridine (3-picoline) into semiconductor layered nanomaterial (MnPS3) was investigated. New conditions were applied. New phases appeared and lattice expansions were 0.36 nm for 2-picoline intercalation and 0.728 nm for 3-picoline intercalation. The XRD (X- ray diffraction) patterns exhibit sharp hkl reflections confirming that the material is highly crystalline. The interlayer gap (0.64 nm) of the host plays a role for the arrangement of the guest in the interlayer region. The crystal structure of the MnPS3 was indexed in the monoclinic system before intercalation. After intercalation, the crystal system was indexed in the trigonal unit cell. The lattice parameters were obtained and c-axis value was related to the (001) reflections.

  18. K-intercalated carbon systems: Effects of dimensionality and substrate

    KAUST Repository

    Kaloni, Thaneshwor P.

    2012-06-01

    Density functional theory is employed to investigate the electronic properties of K-intercalated carbon systems. Young\\'s modulus indicates that the intercalation increases the intrinsic stiffness. For K-intercalated bilayer graphene on SiC(0001) the Dirac cone is maintained, whereas a trilayer configuration exhibits a small splitting at the Dirac point. Interestingly, in contrast to many other intercalated carbon systems, the presence of the SiC(0001) substrate does not suppress but rather enhances the charge carrier density. Reasonably high values are found for all systems, the highest carrier density for the bilayer. The band structure and electron-phonon coupling of free-standing K-intercalated bilayer graphene points to a high probability for superconductivity in this system. © 2012 Europhysics Letters Association.

  19. Improvement on stability of square planar rhodium (Ⅰ) complexes for carbonylation of methanol to acetic acid

    Institute of Scientific and Technical Information of China (English)

    蒋华; 潘平来; 袁国卿; 陈新滋

    1999-01-01

    A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces the investment on the equipment.

  20. High pressure measurement of the uniaxial stress of host layers on intercalants and staging transformation of intercalation compounds

    CERN Document Server

    Park, T R; Kim, H; Min, P

    2002-01-01

    A layered double-hydroxide intercalation compound was synthesized to measure the uniaxial stress the host layers exert on the intercalants. To measure the uniaxial stress, we employed the photoluminescence (PL) from the intercalated species, the Sm ion complex, as it is sensitive to the deformation of the intercalants. Of the many PL peaks the Sm ion complex produces, the one that is independent of the counter-cation environment was chosen for the measurement since the Sm ion complexes are placed under a different electrostatic environment after intercalation. The peak position of the PL was redshifted linearly with increasing hydrostatic pressure on the intercalated sample. Using this pressure-induced redshifting rate and the PL difference at ambient pressure between the pre-intercalation and the intercalated ions, we found that, in the absence of external pressure, the uniaxial stress exerted on the samarium ion complexes by the host layers was about 13.9 GPa at room temperature. Time-resolved PL data also ...

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

    Science.gov (United States)

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

    2013-07-01

    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 CO32- solutions imply that Mg3Al-VC LDH is a better controlled release system than Mg3Fe-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 CO32- solution.

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

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Xiaorui, E-mail: gxr_1320@sina.com [College of Science, Hebei University of Engineering, Handan 056038 (China); School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA (United Kingdom); Lei, Lixu [School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); O' Hare, Dermot [Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA (United Kingdom); Xie, Juan [College of Science, Hebei University of Engineering, Handan 056038 (China); Gao, Pengran [School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); Chang, Tao [College of Science, Hebei University of Engineering, Handan 056038 (China)

    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.

  3. Electrochemical study of {beta}-diketonatobis(triphenylphosphite)rhodium(I) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Erasmus, Johannes J.C. [Department of Chemistry, PO Box 339, University of the Free State, Bloemfontein 9300 (South Africa); Conradie, Jeanet, E-mail: conradj@ufs.ac.z [Department of Chemistry, PO Box 339, University of the Free State, Bloemfontein 9300 (South Africa)

    2011-10-30

    Highlights: > Rh(I) is electrochemically irreversible oxidized to Rh(III) in [Rh(RCOCHCOR')(P(OPh){sub 3}){sub 2}]. > Oxidation potentials E{sub pa}(Rh) and kinetic oxidative addition rate constants relate linearly. > Hammett {sigma} values, group electronegativities and the Lever ligand parameter relate to E{sub pa}(Rh). - Abstract: The electrochemical behaviour of the series of ten [Rh(RCOCHCOR')(P(OPh){sub 3}){sub 2}] complexes with R, R' = CF{sub 3}, CF{sub 3} (1), CF{sub 3}, CH{sub 3} (2), CF{sub 3}, Ph (C{sub 6}H{sub 5}) (3), CF{sub 3}, Fc (ferrocenyl = (C{sub 5}H{sub 5})Fe(C{sub 5}H{sub 4})) (4), CH{sub 3}, Ph (5), CH{sub 3}, CH{sub 3} (6), Ph, Ph (7), Fc, CH{sub 3} (8), Fc, Ph (9) and Fc, Fc (10) were studied in acetonitrile containing 0.100 mol dm{sup -3} tetra-n-butylammonium hexafluorophosphate as supporting electrolyte utilizing a glassy carbon working electrode. Results are consistent with Rh(I) being first oxidized in an electrochemically irreversible two-electron transfer process at peak anodic potentials ranging E{sub pa}(Rh) = 0.124-0.881 V vs. Fc/Fc{sup +}. For the ferrocene-containing complexes (4), and (8)-(10) the rhodium oxidation was followed by the electrochemically reversible oxidation of the ferrocenyl group in a one-electron transfer process at a slightly more positive potential. Relationships were established between the electrochemical quantity E{sub pa}(Rh) and kinetic parameter log k{sub 2} as well the sum of experimental group electronegativities (Gordy Scale) of the R and R' groups ({chi}{sub R} + {chi}{sub R'}), the Hammett {sigma} values ({sigma}{sub R} + {sigma}{sub R'}) and the Lever ligand parameter E{sub L} for the [Rh(RCOCHCOR')(P(OPh){sub 3}){sub 2}] complexes: E{sub pa}(Rh) (vs. Fc/Fc{sup +}/V) = 0.31 ({chi}{sub R} + {chi}{sub R'})-1.09 = 0.56 ({sigma}{sub R} + {sigma}{sub R'}) + 0.28 = S{sub M} ({Sigma}E{sub L}) + (I{sub M} - 0.66 V) = -0.23 log k{sub 2} - 0.03 (k{sub 2

  4. Alkali-metal intercalation in carbon nanotubes

    Science.gov (United States)

    Béguin, F.; Duclaux, L.; Méténier, K.; Frackowiak, E.; Salvetat, J. P.; Conard, J.; Bonnamy, S.; Lauginie, P.

    1999-09-01

    We report on successful intercalation of multiwall (MWNT) and single wall (SWNT) carbon nanotubes with alkali metals by electrochemical and vapor phase reactions. A LiC10 compound was produced by full electrochemical reduction of MWNT. KC8 and CsC8-MWNT first stage derivatives were synthesized in conditions of alkali vapor saturation. Their identity periods and the 2×2 R 0° alkali superlattice are comparable to their parent graphite compounds. The dysonian shape of KC8 EPR line and the temperature-independent Pauli susceptibility are both characteristic of a metallic behavior, which was confirmed by 13C NMR anisotropic shifts. Exposure of SWNT bundles to alkali vapor led to an increase of the pristine triangular lattice from 1.67 nm to 1.85 nm and 1.87 nm for potassium and rubidium, respectively.

  5. Electrical Properties of Expanded Graphite Intercalation Compounds

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The intercalation compounds of CuCl2 were synthesized with expanded graphite, whose magnitude of the electrical conductivity is about 103S.cm-1. Their electrical conductivity is 3~6 times as high as that of the expanded graphite, and about 10 times as high as that of GIC made of the non-expanded graphite. The microanalysis results of chemical compounds by X-ray energy spectrum scanning of TEM testified that the atomic ratio of chloride and cupric is nonstoichoimetric. The multivalence and exchange of electrovalence of the cupric ion was confirmed by the XPS-ESCA. Vacancy of chlorine anion increases the concentration of charge carrier.The special stage structure, made of graphite and chloride, produces a weak chemical bond belt and provides a carrier space in the direction of GIC layer. These factors develop the electrical properties.

  6. Intercalation compounds involving inorganic layered structures

    Directory of Open Access Journals (Sweden)

    CONSTANTINO VERA R. L.

    2000-01-01

    Full Text Available Two-dimensional inorganic networks can shown intracrystalline reactivity, i.e., simple ions, large species as Keggin ions, organic species, coordination compounds or organometallics can be incorporated in the interlayer region. The host-guest interaction usually causes changes in their chemical, catalytic, electronic and optical properties. The isolation of materials with interesting properties and making use of soft chemistry routes have given rise the possibility of industrial and technological applications of these compounds. We have been using several synthetic approaches to intercalate porphyrins and phthalocyanines into inorganic materials: smectite clays, layered double hydroxides and layered niobates. The isolated materials have been characterized by elemental and thermal analysis, X-ray diffraction, surface area measurements, scanning electronic microscopy, electronic and resonance Raman spectroscopies and EPR. The degree of layer stacking and the charge density of the matrices as well their acid-base nature were considered in our studies on the interaction between the macrocycles and inorganic hosts.

  7. Synthesis and characterization of bulky mesoporous silica Pd-MCM-41

    International Nuclear Information System (INIS)

    Bulky palladium catalyst supported on mesoporous silica MCM-41 (Pd-MCM-41) was successfully synthesized by hydrothermal hot-pressing method. In this study, the structure of the palladium species in Pd-MCM-41 bulk before and after heat-treatment process was revealed by X-ray diffraction (XRD), X-ray absorption near edge structure (XANES) and transmission electron microscopy (TEM). Also, the microstructure and mesoporous property of Pd-MCM-41 bulk was discussed. As a result, it was revealed that these dense Pd-MCM-41 bulks possessed a high surface area of over 1000 m2/g and the structure of palladium of Pd-MCM-41 bulk is almost equal to palladium (0) metal. (author)

  8. Photoinduced and thermal denitrogenation of bulky triazoline crystals: insights into solid-to-solid transformation.

    Science.gov (United States)

    de Loera, Denisse; Stopin, Antoine; Garcia-Garibay, Miguel A

    2013-05-01

    The photoinduced and thermal denitrogenation of crystalline triazolines with bulky substituents leads to the quantitative formation of aziridines in clean solid-to-solid reactions despite very large structural changes in the transition from reactant to product. Analysis of the reaction progress by powder X-ray diffraction, solid-state (13)C CPMAS NMR, solid-state FTIR spectroscopy, and thermal analysis has revealed that solid-to-solid reactions proceed either through metastable phases susceptible to amorphization or by mechanisms that involve a reconstructive phase transition that culminates in the formation of the stable phase of the product. While the key for a solid-to-solid transformation is that the reaction occurs below the eutectic temperature of the reactant and product two-component system, experimental evidence suggests that those reactions will undergo a reconstructive phase transition when they take place above the glass transition temperature. PMID:23547729

  9. Maternal diet and dioxin-like activity, bulky DNA adducts and micronuclei in mother newborns

    DEFF Research Database (Denmark)

    Pedersen, Marie; Halldorsson, Thorhallur I; Autrup, Herman;

    2012-01-01

    Maternal diet can contribute to carcinogenic exposures and also modify effects of environmental exposures on maternal and fetal genetic stability. In this study, associations between maternal diet and the levels of dioxin-like plasma activity, bulky DNA adducts in white blood cells and micronuclei...... (MN) in lymphocytes from mother to newborns were examined. From 98 pregnant women living in the greater area of Copenhagen, Denmark in 2006-2007, maternal peripheral blood and umbilical cord blood were collected, together with information on health, environmental exposure and lifestyle. Maternal diet...... was estimated on the basis of maternal food frequency questionnaire (FFQ) completed by the end of pregnancy. Biomarkers were detected in paired blood samples through the dioxin-responsive chemical-activated luciferase expression (CALUX)(®) bioassay, (32)P-postlabelling technique and cytokinesis-block MN assay...

  10. Distance-Dependent Attractive and Repulsive Interactions of Bulky Alkyl Groups.

    Science.gov (United States)

    Hwang, Jungwun; Li, Ping; Smith, Mark D; Shimizu, Ken D

    2016-07-01

    The stabilizing and destabilizing effects of alkyl groups on an aromatic stacking interaction were experimentally measured in solution. The size (Me, Et, iPr, and tBu) and position (meta and para) of the alkyl groups were varied in a molecular balance model system designed to measure the strength of an intramolecular aromatic interaction. Opposite stability trends were observed for alkyl substituents at different positions on the aromatic rings. At the closer meta-position, smaller groups were stabilizing and larger groups were destabilizing. Conversely, at the farther para-position, the larger alkyl groups were systematically more stabilizing with the bulky tBu group forming the strongest stabilizing interaction. X-ray crystal structures showed that the stabilizing interactions of the small meta-alkyl and large para-alkyl groups were due to their similar distances and van der Waals contact areas with the edge of opposing aromatic ring. PMID:27159670

  11. Synthesis and characterization of Mn intercalated Mg-Al hydrotalcite.

    Science.gov (United States)

    Yang, Chengxue; Liao, Libing; Lv, Guocheng; Wu, Limei; Mei, Lefu; Li, Zhaohui

    2016-10-01

    Mn intercalated hydrotalcite was prepared using a reconstruction method. And Mn intercalation was confirmed by XRD, FTIR, and thermal analyses. The different valences of Mn were present as determined by XPS. Calcination slightly promoted the isomorphic replacement of Mn(2+) and Mn(3+) for Mg(2+) and Al(3+), especially the replacement of Mn(2+) for Mg(2+) and Al(3+), and to some extent, reduced Mn intercalation. Ultrasonic treatment significantly increased Mn intercalation in permanganate form (Mn(7+)), and promoted the replacement of Mn(2+) for Mg(2+) and Al(3+). XRF analysis showed that ultrasonic treatment decreased the unbalanced layer charge of Mn intercalated hydrotalcite, while prolonged calcination increased it. These results may provide guidance on the preparation and application of Mn intercalated hydrotalcite. Extended calcination time and ultrasonic vibration increased the interlayer spacing of hydrotalcite, as a result of reduction in layer charge. As the layer charge was not completely balanced after Mn intercalation, a certain amount of CO3(2-) was re-adsorbed into the interlayer space. Mn-hydrotalcites with different layer charges, different contents of Mn with varying valences are expected to have different performances in the process of adsorption, degradation, and catalysis. PMID:27380016

  12. Synthesis and Electroluminescent Properties of Julolidine-π-Juloidine Type Materials with the Bulky Adamantane Groups

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kum Hee; Yoon, Seung Soo [Sungkyunkwan Univ., Suwon (Korea, Republic of); Lee, Seok Jae; Kim, Young Kwan [Hongik Univ., Seoul (Korea, Republic of)

    2012-11-15

    A main problem of red emitting material, which contributes to their low EL performances, is the concentration quenching due to the effective self aggregation and the consequent formation of excimers. To avoid this drawback and thus improve the EL properties of red fluorescent OLED devices, many synthetic efforts have been conducted to develop new emitting materials with the structural motifs to suppress self-aggregation by the weakening intermolecular attractive interactions. Particularly, the introduction of bulky moieties in the emitters would provide the steric hindrance between emitting materials in solid state devices and thus reduce the self-aggregation. Nevertheless, EL performances of red materials still need to be improved for the practical applications. In conclusion, we designed and synthesized three julolidine-π-juloidine type emitting materials (1-3) with the bulky adamantane groups. To study their electroluminescent properties, the multilayered OLED devices with the structure of ITO/NPB (40 nm)/ADN : 1-3 (x%) (20 nm)/Alq{sub 3} (40 nm)/Liq (2 nm)/Al were fabricated. All devices using emitters 1-3 showed the efficient emissions, in which their EL performances depend on the structure of emitters sensitively. Particularly, a device using emitter 3 exhibited the efficient orange-red emission with the luminous and power efficiencies of 4.79 cd/A and 1.76 lm/W at 20 mA/cm{sup 2}, respectively. The CIE coordinates of this device was (0.57, 0.42) at 7.0 V.

  13. Lifestyle, Environmental, and Genetic Predictors of Bulky DNA Adducts in a Study Population Nested within a Prospective Danish Cohort

    DEFF Research Database (Denmark)

    Eriksen, K. T.; Sørensen, M.; Autrup, H.;

    2010-01-01

    Danish cohort. At enrollment, blood samples were collected and information on lifestyle, including dietary and smoking habits, obtained. Previously, bulky DNA adducts were measured in 245 individuals who developed lung cancer and 255 control members of the cohort. Of these 500 individuals, data on 375...... found between dietary factors or smoking and DNA adduct levels. Further, the results showed no prominent associations between any of 12 genetic polymorphisms and adduct levels. Overall, our study showed only few associations between dietary, environmental, and genetic factors and levels of bulky DNA...

  14. Olefins hydro-formylation catalysed by rhodium complexes using ionic liquids; Hydroformylation des olefines par les complexes du rhodium dans les liquides ioniques

    Energy Technology Data Exchange (ETDEWEB)

    Favre, F.

    2000-10-26

    Biphasic long chain olefins hydro-formylation catalysed by rhodium complexes using ionic liquids allows a selective reaction and an easy separation of the products from the catalyst. This study reports the synthesis of ionic liquids that were used as the catalyst's solvent. Their physical and chemical properties (melting point, solubility of organic substrates) can be varied with the structure of the organic cation (imidazolium, pyridinium, pyrrolydinium) and with its substituents (nature, length, number). It depends also on the nature of the inorganic anion (hexa-fluoro-phosphate, tetrafluoroborate, tri-fluoro-acetate, triflate, bistriflylamidure...). The use of phosphorus ligands bearing ionic functions proved to be efficient to maintain the onerous rhodium catalyst in the ionic liquid phase. Phosphines, phosphites and phosphinites including anionic (sulfonate, carboxylate) or cationic (imidazolium, pyridinium, guanidinium, phosphonium) groups have been synthesised. Finally, the influences of the ligand and of the ionic liquid on the catalytic system performances are described. Selectivities in aldehydes and reaction rates proved to be highly dependent on the nature of the ligand and of the ionic liquid. The different possibilities of recycling the ionic phase containing the rhodium catalyst have been also studied. (author)

  15. Amine-intercalated α-zirconium phosphates as lubricant additives

    International Nuclear Information System (INIS)

    In this study, three types of amines intercalated α-zirconium phosphate nanosheets with different interspaces were synthesized and examined as lubricant additives to a mineral oil. Results from tribological experiments illustrated that these additives improved lubricating performance. Results of rheological experiments showed that the viscosity of the mineral oil was effectively reduced with the addition of α-zirconium phosphate nanosheets. The two-dimensional structure, with larger interspaces, resulting from amine intercalation, exhibited improved effectiveness in reducing viscosity. This study demonstrates that the nanosheet structure of α-zirconium phosphates is effective in friction reduction. The manufacture of lubricants with tailored viscosity is possible by using different intercalators

  16. Prediction of superconductivity in Li-intercalated bilayer phosphorene

    Energy Technology Data Exchange (ETDEWEB)

    Huang, G. Q. [Department of Physics, Nanjing Normal University, Nanjing 210023 (China); National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Xing, Z. W., E-mail: zwxing@nju.edu.cn [National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Xing, D. Y. [National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Collaborative Innovation Center of Advanced Microstructures and Department of Physics, Nanjing University, Nanjing 210093 (China)

    2015-03-16

    It is shown that bilayer phosphorene can be transformed from a direct-gap semiconductor to a BCS superconductor by intercalating Li atoms. For the Li-intercalated bilayer phosphorene, we find that the electron occupation of Li-derived band is small and superconductivity is intrinsic. With increasing the intercalation of Li atoms, both increased metallicity and strong electron-phonon coupling are favorable for the enhancement of superconductivity. The obtained electron-phonon coupling λ can be larger than 1 and the superconducting temperature T{sub c} can be increased up to 16.5 K, suggesting that phosphorene may be a good candidate for a nanoscale superconductor.

  17. Electrochemical synthesis of alkali-intercalated iron selenide superconductors

    Institute of Scientific and Technical Information of China (English)

    申士杰; 应天平; 王刚; 金士锋; 张韩; 林志萍; 陈小龙

    2015-01-01

    Electrochemical method has been used to insert K/Na into FeSe lattice to prepare alkali-intercalated iron selenides at room temperature. Magnetization measurement reveals that KxFe2Se2 and NaxFe2Se2 are superconductive at 31 K and 46 K, respectively. This is the first successful report of obtaining metal-intercalated FeSe-based high-temperature superconductors using electrochemical method. It provides an effective route to synthesize metal-intercalated layered compounds for new superconductor exploration.

  18. The Dynamic Viscoelasticity of Polyethylene Based Montmorillonite Intercalated Nanocomposites

    Institute of Scientific and Technical Information of China (English)

    Hong Mei YANG; Qiang ZHENG

    2004-01-01

    The viscoelastic behavior of melts for two systems composed of intercalated nanocomposites based on low density polyethylene and 3 wt% loading of cetyltrimethyl-ammonium bromide modified montmorillonite was studied. The results obtained through examining the dynamic storage module G'and dynamic loss module G" values of the composite revealed that the dynamic viscoelastic properties of composite strongly depended on intercalation of polymer, and exhibited dramatically change with altering intercalation conditions. Only when modified montmorillonite content was about 3 wt%, the composite showed a trend of pseudo-solidlike at lower frequencies.

  19. Electrochemical Intercalation of Sodium into Silicon Thin Film

    Institute of Scientific and Technical Information of China (English)

    Dong-Yeon Kim; Hyo-Jun Ahn; Gyu-Bong Cho; Jong-Seon Kim; Ho-Suk Ryu; Ki-Won Kim; Jou-Hyeon Ahn; Won-Cheol Shin

    2008-01-01

    In order to investigate the possibility of Si thin film as an anode for Na battery, we studied the electrochemical intercalation of sodium into the Si film. Amorphous Si thin film electrode was prepared using DC magnetron sputtering. Sodium ion could intercalate into Si thin film upto Na0.52Si, i.e. 530mAh · g-1-Si. The first discharge capacity was 80mAh.·g-1-Si, which meant reversible amount of sodium intercalation. The discharge capacity slightly decreased to 70mAh · g-1-Si after 10 cycles.

  20. Graphene oxide based chiral diamine rhodium catalyst for asymmetric transfer hydrogenation of aromatic ketones

    Directory of Open Access Journals (Sweden)

    LIU Ketang

    2013-02-01

    Full Text Available Functional graphite oxide materials were synthesized through the Hummers chemical oxidation of graphite.Heterogeneous catalyst was prepared via direct grafting diamine-based chiral ligand to graphite oxide followed by the complexation with organorhodium complex.Such a chiral rhodium catalyst exhibited high catalytic activity and enantioselectivity in asymmetric transfer hydrogenation of aromatic ketones in aqueous medium under mild condition.

  1. Regio- and Diasteroselectivity of Rhodium-catalyzed Ring Opening Reaction of Oxabenzonorbornadienes with Heteroatom Nucleophiles

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A new rhodium catalyzed ring opening reaction of oxabenzonorbornadienes and its derivatives was described. This reaction forms a new carbon-nitrogen bond via an intermolecular allylic displacement of the bridgehead oxygen with a piperazine's derivatives, which proceeds with very high regioselectivity.

  2. The Role of the Element Rhodium in the Hyperbolic Law of the Periodic Table of Elements

    Directory of Open Access Journals (Sweden)

    Albert Khazan

    2008-07-01

    Full Text Available The role of the element rhodium as an independent affirmation of calculations by the Hyperbolic Law and validity of all its relations is shown herein. The deviation in calculation by this method of the atomic mass of heaviest element is 0.0024%, and its coefficient of scaling 0.001-0.005%.

  3. Rhodium Nanoparticle Shape Dependence in the Reduction of NO by CO

    Energy Technology Data Exchange (ETDEWEB)

    Renzas, J.R.; Zhang, Y.; Huang, W.; Somorjai, G.A.

    2009-07-13

    The shape dependence of the catalytic reduction of NO by CO on Rhodium nanopolyhedra and nanocubes was studied from 230-270 C. The nanocubes are found to exhibit higher turnover frequency and lower activation energy than the nanopolyhedra. These trends are compared to previous studies on Rh single crystals.

  4. Double-spin-flip resonance of rhodium nuclei at positive and negative spin temperatures

    DEFF Research Database (Denmark)

    Tuoriniemi, J.T.; Knuuttila, T.A.; Lefmann, K.;

    2000-01-01

    Sensitive SQUID-NMR measurements were used to study the mutual interactions in the highly polarized nuclear-spin system of rhodium metal. The dipolar coupling gives rise to a weak double-spin-flip resonance. The observed frequency shifts allow deducing separately the dipolarlike contribution...

  5. Azido[1,1'-bis(diphenylphosphino)ferrocene](pentamethylcyclopentadienyl)rhodium(III) hexafluorophosphate.

    Science.gov (United States)

    Han, Won Seok; Lee, Soon W

    2004-04-01

    In the title compound, azido-2kappaN-bis[micro-(1eta(5):2kappaP)-diphenylphosphinocyclopentadienyl][2(eta(5))-pentamethylcyclopentadienyl]iron(III)rhodium(III) hexafluorophosphate, [[Rh(C(10)H(15))(N(3))][Fe(micro-C(17)H(14)P)(2)

  6. A new class of rhodium complexes containing free donor atoms and their intramolecular substitution reaction

    Institute of Scientific and Technical Information of China (English)

    JIANG, Hua; YUAN, Guo-Qing; ZHANG, Shu-Feng; PAN, Ping-Lai; DIAO, Kai-Sheng

    2000-01-01

    A new class of rhodium complexes with high catalytic activity as well as excellent stability, which was used as catalyst for carlbonylation of methanol to acetic acid, is reported. It con tains free donor (namely un-coordinated donor) atoms which enable to improve its stability by intramolecular substitution rearction. Its synthesis, characteristic and catalytic reaction were discussed here.

  7. Immobilization of rhodium complexes at thiolate monolayers on gold surfaces : Catalytic and structural studies

    NARCIS (Netherlands)

    Belser, T; Stöhr, Meike; Pfaltz, A

    2005-01-01

    Chiral rhodium-diphosphine complexes have been incorporated into self-assembled thiolate monolayers (SAMS) on gold colloids. Catalysts of this type are of interest because they combine properties of homogeneous and heterogeneous systems. In addition, it should be possible to influence the catalytic

  8. Komplexe zouten van trans-1-2-diaminocyclohexaan met driewaardig rhodium en kobalt

    NARCIS (Netherlands)

    Bijkerk, Lucas

    1937-01-01

    Some complex salts of trans-I-2-díominocyclohexane with trivalent cobaltum and rhodium were prepared and their properties described in detail. Diaminocyclohexanwe as obtained by the following series of reactions: cyclohexanone --> cyclohexanone-I-oxalylicester --> cyclohexonone-I-carboxylicester-2 -

  9. Monodentate phosphoramidites : A breakthrough in rhodium-catalysed asymmetric hydrogenation of olefins

    NARCIS (Netherlands)

    Berg, Michel van den; Minnaard, Adriaan J.; Haak, Robert M.; Leeman, Michel; Schudde, Ebe P.; Meetsma, Auke; de Vries, Andre H.M.; Maljaars, C. Elizabeth P.; Willans, Charlotte E.; Hyett, David; Boogers, Jeroen A.F.; Henderickx, Hubertus; Feringa, Ben L.

    2003-01-01

    Monodentate phosphoramidites based on BINOL or substituted BINOL are excellent ligands for the rhodium-catalysed asymmetric hydrogenation of olefins. Very high enantioselectivities were obtained with MonoPhos (7a) the simplest member of this class, a ligand that is prepared in a single step from BIN

  10. Strain Lattice Imprinting in Graphene by C60 Intercalation at the Graphene/Cu Interface

    NARCIS (Netherlands)

    Monazami, Ehsan; Bignardi, Luca; Rudolf, Petra; Reinke, Petra

    2015-01-01

    Intercalation of C60 molecules at the graphene-substrate interface by annealing leads to amorphous and crystalline intercalated structures. A comparison of topography and electronic structure with wrinkles and moiré patterns confirms intercalation. The intercalated molecules imprint a local strain/d

  11. Intercalated samarium as an agent enabling the intercalation of oxygen under a monolayer graphene film on iridium

    Science.gov (United States)

    Afanas'eva, E. Yu.; Rut'kov, E. V.; Gall', N. R.

    2016-06-01

    Using thermal desorption time-of-flight mass spectrometry and thermionic methods, it is shown that oxygen does not intercalate under a graphene monolayer grown correctly on iridium, at least at temperatures of T = 300-400 K and exposures below 12000 L. However, if the graphene film on iridium is preliminary intercalated with samarium atoms (up to coverage of θSm = 0.2-0.45), the penetration of oxygen atoms under the graphene film is observed. The oxygen atoms in the intercalated state are chemically bonded to samarium atoms and remain under graphene up to high temperatures (~2150 K).

  12. Influence of interlayer cations on organic intercalation of montmorillonite.

    Science.gov (United States)

    Wu, Limei; Liao, Libing; Lv, Guocheng

    2015-09-15

    The influence of the types of interlayer cations on organic intercalation of montmorillonite (Mt) was studied in this paper. The distribution of Na(+), K(+), Mg(2+), Ca(2+) and Fe(3+) in montmorillonite interlayer, their interaction with structure layers and the effect of interlayer cations on the basal spacing of Mt, the amount of binding water for different interlayer cations and the binding force between them were investigated systematically. 1-Hexadecy1-3-methylimidazolium chloride monohydrate (C16mimCl) was intercalated into montmorillonites with different interlayer cations. The influence of interlayer cations on organic intercalation was investigated. Molecular dynamics (MD) modeling was used to speculate the interlayer microstructures of the organically intercalated Mt with different interlayer cations. These simulations help to predict the microstructure of organo-Mt and guide their relevant engineering applications. PMID:26001131

  13. Intercalation of Carbon Nanotube Fibers to Improve their Conductivity Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This proposed research will explore how NASA intercalation technology can be used to lower the resistivity of the new Rice-Teijin fiber make them viable for NASA...

  14. Electronic spectra of anions intercalated in layered double hydroxides

    Indian Academy of Sciences (India)

    S Radha; P Vishnu Kamath

    2013-10-01

    Transition metal complexes intercalated in layered double hydroxides have a different electronic structure as compared to their free state owing to their confinement within the interlayer gallery. UV–Vis absorptions of the intercalated complex anions show a significant shift as compared to their free state. The ligand to metal charge transfer transitions of the ferricyanide anion show a red shift on intercalation. The ferrocyanide ion shows a significant blue shift of – bands due to the increased separation between 2g and g levels on intercalation. MnO$^{-}_{4}$ ion shows a blue shift in its ligand to metal charge transfer transition since the non-bonding 1 level of oxygen from which the transition arises is stabilized.

  15. Graphene on Mica - Intercalated Water Trapped for Life

    OpenAIRE

    Ochedowski, O.; B. Kleine Bussmann; Schleberger, M.

    2014-01-01

    In this work we study the effect of thermal processing of exfoliated graphene on mica with respect to changes in graphene morphology and surface potential. Mild annealing to temperatures of about 200°C leads to the removal of small amounts of intercalated water at graphene edges. By heating to 600°C the areas without intercalated water are substantially increased enabling a quantification of the charge transfer properties of the water layer by locally resolved Kelvin probe force microscopy da...

  16. A molecular model for proflavine-DNA intercalation.

    OpenAIRE

    Neidle, S; Pearl, L H; Herzyk, P; Berman, H M

    1988-01-01

    A molecular model has been derived for the intercalation of proflavine into the CpG site of the decamer duplex of d(GATACGATAC). The starting geometry of the intercalation site was taken from previous crystallographic studies on the d(CpG)-proflavine complex, and molecular mechanics used to obtain a stereochemically acceptable structure. This has widened grooves compared to standard A- or B- double helices, as well as distinct conformational, roll, twist and tilt features.

  17. A New Tin Graphite Intercalation Compound for Lithium Ion Batteries

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A new composite material was fabricated by intercalating tin nanoparticles into graphite. The tin graphite intercalation compound(Sn-GIC) was prepared by the interactions of tin tetrachloride with KC8 (K-GIC) in tetrahydrofuran good cycling performance in comparison with Sn and SnO2, it suggests that the association of tin with graphite not only improves the reversible capacities, but also prevents the volume changes resulted from lithium insertion and extraction with tin during a charge-discharge process.

  18. Thermodynamics of Lithium Intercalation into Graphites and Disordered Carbons

    OpenAIRE

    Reynier, Y. F.; Yazami, R.; Fultz, B.

    2004-01-01

    The temperature dependence of the open-circuit potential of lithium half-cells was measured for electrodes of carbon materials having different amounts of structural disorder. The entropy of lithium intercalation, DeltaS, and enthalpy of intercalation, DeltaH, were determined over a broad range of lithium concentrations. For the disordered carbons, DeltaS is small. For graphite, an initially large DeltaS decreases with lithium concentration, becomes negative, and then shows two plateaus assoc...

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

    Science.gov (United States)

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

    2016-04-12

    The regioselective double hydrophosphination of alkynes mediated by rhodium catalysts is presented. The distinctive stereoelectronic properties of the NHC ligand prevent the catalyst deactivation by diphosphine coordination thereby allowing for the closing of a productive catalytic cycle. PMID:27022648

  20. The concise synthesis of chiral tfb ligands and their application to the rhodium-catalyzed asymmetric arylation of aldehydes

    OpenAIRE

    Nishimura, Takahiro; Kumamoto, Hana; Nagaosa, Makoto; Hayashi, Tamio

    2009-01-01

    New C2-symmetric tetrafluorobenzobarrelene ligands were prepared and applied successfully to the rhodium-catalyzed asymmetric addition of arylboronic acids to aromatic aldehydes giving chiral diarylmethanols in high yield with high enantioselectivity.

  1. Effect of deuterium ion beam irradiation onto the mirror-like pulsed laser deposited thin films of rhodium

    Energy Technology Data Exchange (ETDEWEB)

    Mostako, A.T.T., E-mail: abu@iitg.ernet.in [Laser and Photonics Lab, Department of Physics, Indian Institute of Technology Guwahati, Guwahati 781039 (India); Khare, Alika [Laser and Photonics Lab, Department of Physics, Indian Institute of Technology Guwahati, Guwahati 781039 (India); Rao, C.V.S.; Vala, Sudhirsinh; Makwana, R.J.; Basu, T.K. [Neutronics Lab, Institute for Plasma Research, Bhat, Gandhinagar 382428 (India)

    2015-01-01

    Highlights: • Rh mirror like thin films are fabricated by PLD technique for FM application. • Rh thin film FMs are irradiated with 10, 20, and 30 keV D ion beam. • Effect of D ion beam irradiation on Rh FM’s reflectivity is investigated. - Abstract: The effect of deuterium ion beam irradiation on the reflectivity of mirror-like pulsed laser deposited (PLD) thin film of rhodium is reported. The deposition parameters; target-substrate distance and background helium gas pressure were optimized to obtain the good quality rhodium films, of higher thickness, oriented preferentially in (1 1 1) plane. The rhodium thin films deposited at optimum PLD parameters were exposed to 10, 20, and 30 keV deuterium ion beam. The changes in surface morphology and UV–Visible–FIR reflectivity of mirror-like rhodium thin films, as a function of energy of deuterium ion beam, after exposure are reported.

  2. Stabilized rhodium(0) nanoparticles: a reusable hydrogenation catalyst for arene derivatives in a biphasic water-liquid system.

    Science.gov (United States)

    Schulz, J; Roucoux, A; Patin, H

    2000-02-18

    A colloidal system based on an aqueous suspension of rhodium(o) nanoparticles proved to be an efficient catalyst for the hydrogenation of arene derivatives under biphasic conditions. The rhodium nanoparticles (2-2.5 nm) were synthesized by the reduction of RhCl3 x 3H2O with sodium borohydride and were stabilized by highly water-soluble N-alkyl-N-(2-hydroxyethyl)ammonium salts (HEA-Cn). These surfactant molecules were characterized by measurements of the surface tension and the aqueous dispersions with rhodium were observed by transmission electron cryomicroscopy. The catalytic system is efficient under ultramild conditions, namely room temperature and 1 atm H2 pressure. The aqueous phase which contains the protected rhodium(0) colloids can be reused without significant loss of activity. The microheterogeneous behavior of this catalytic system was confirmed on a mercury poisoning experiment.

  3. Asymmetric synthesis of gem-diaryl substituted cyclic sulfamidates and sulfamides by rhodium-catalyzed arylation of cyclic ketimines.

    Science.gov (United States)

    Nishimura, Takahiro; Ebe, Yusuke; Fujimoto, Hiroto; Hayashi, Tamio

    2013-06-18

    Asymmetric addition of arylboronates to aryl-substituted cyclic ketimines proceeded in the presence of a rhodium catalyst coordinated with a chiral diene ligand to give high yields of sulfamidates and sulfamides with high enantioselectivity (up to 99% ee).

  4. Intercalation mechanisms of lithium into graphitized needle cokes

    Institute of Scientific and Technical Information of China (English)

    苏玉长; 尹志民; 徐仲榆

    2001-01-01

    A needle coke was graphitized at different heat treatment temperature (2000℃ to 3000℃). The electrochemical intercalation mechanism of Li into the graphitized coke has been studied in Li|1mol*L-1 LiClO4+ethylene carbonate/diethylene carbonate|graphite cells, using an in-situ X-Ray diffraction (XRD) technique. The study of Li-C intercalation processes of the graphitized coke reveals that there are three major types of intercalation behavior. The first is uniformly intercalated at all Li-C compounds in graphitized coke heated at 2250℃; the second is obviously staging phenomenon during intercalating for the graphitized coke heated at 2750℃; the third is cointercalation of solvated Li-ion at high potential (>0.3V) and then lithium electrochemical intercalation at lower potential for that heated at 3000℃, resulting in the decrease of capacity and efficiency of graphite negative electrode for lithium-ion secondary battery.

  5. Genotoxicity of non-covalent interactions: DNA intercalators

    Energy Technology Data Exchange (ETDEWEB)

    Ferguson, Lynnette R. [Auckland Cancer Society Research Centre, Faculty of Medical and Health Science, University of Auckland (New Zealand)], E-mail: l.ferguson@auckland.ac.nz; Denny, William A. [Auckland Cancer Society Research Centre, Faculty of Medical and Health Science, University of Auckland (New Zealand)

    2007-10-01

    This review provides an update on the mutagenicity of intercalating chemicals, as carried out over the last 17 years. The most extensively studied DNA intercalating agents are acridine and its derivatives, that bind reversibly but non-covalently to DNA. These are frameshift mutagens, especially in bacteria and bacteriophage, but do not otherwise show a wide range of mutagenic properties. Di-acridines or di-quinolines may be either mono- or bis-intercalators, depending upon the length of the alkyl chain separating the chromophores. Those which monointercalate appear as either weak frameshift mutagens in bacteria, or as non-mutagens. However, some of the bisintercalators act as 'petite' mutagens in Saccharomyces cerevisiae, suggesting that they may be more likely to target mitochondrial as compared with nuclear DNA. Some of the new methodologies for detecting intercalation suggest this may be a property of a wider range of chemicals than previously recognised. For example, quite a number of flavonoids appear to intercalate into DNA. However, their mutagenic properties may be dominated by the fact that many of them are also able to inhibit topoisomerase II enzymes, and this property implies that they will be potent recombinogens and clastogens. DNA intercalation may serve to position other, chemically reactive molecules, in specific ways on the DNA, leading to a distinctive (and wider) range of mutagenic properties, and possible carcinogenic potential.

  6. Genotoxicity of non-covalent interactions: DNA intercalators

    International Nuclear Information System (INIS)

    This review provides an update on the mutagenicity of intercalating chemicals, as carried out over the last 17 years. The most extensively studied DNA intercalating agents are acridine and its derivatives, that bind reversibly but non-covalently to DNA. These are frameshift mutagens, especially in bacteria and bacteriophage, but do not otherwise show a wide range of mutagenic properties. Di-acridines or di-quinolines may be either mono- or bis-intercalators, depending upon the length of the alkyl chain separating the chromophores. Those which monointercalate appear as either weak frameshift mutagens in bacteria, or as non-mutagens. However, some of the bisintercalators act as 'petite' mutagens in Saccharomyces cerevisiae, suggesting that they may be more likely to target mitochondrial as compared with nuclear DNA. Some of the new methodologies for detecting intercalation suggest this may be a property of a wider range of chemicals than previously recognised. For example, quite a number of flavonoids appear to intercalate into DNA. However, their mutagenic properties may be dominated by the fact that many of them are also able to inhibit topoisomerase II enzymes, and this property implies that they will be potent recombinogens and clastogens. DNA intercalation may serve to position other, chemically reactive molecules, in specific ways on the DNA, leading to a distinctive (and wider) range of mutagenic properties, and possible carcinogenic potential

  7. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    Science.gov (United States)

    Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

    2011-07-12

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  8. Study of cerium-promoted rhodium alumina catalyst as a steam reforming catalyst for treatment of spent solvents

    Institute of Scientific and Technical Information of China (English)

    Hee-Chul Yang; Min-Woo Lee; Ho-Sang Hwang; Jei-Kwon Moon; Dong-Yong Chung

    2014-01-01

    This study attempted to develop an appropriate catalyst used for the steam reforming of gasified spent solvents. Rh2O3/ CeO2-Al2O3 catalysts with various CeO2 loadings were prepared and heated at different temperatures of 500 and 800 ºC, and their surface properties were studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron mi-croscopy (TEM), temperature programmed reduction (TPR) and Brumauer-Emmett-Teller (BET) analyses. Rhodium existed in the form of Rh2O3, regardless of the sample composition as well as the heating temperature. In the tested range of cerium addition (up to 12 times the rhodium mass), no significant changes in BET surface areas and binding energy corresponding to Rh 3d5/2were observed. Instead, the addition of cerium led to a greatly enhanced dispersion of rhodium nanoparticles, and no agglomeration of rhodium was observed for samples heated even at 800 ºC. Honeycomb monolith rhodium catalysts promoted with cerium were fabricated and tested for the steam reforming of a gasified spent solvent, mainly consisting of butylene (C4H8). The test results suggested that a ce-rium-promoted rhodium catalyst could be used as an appropriate reforming catalyst for treating low-quality non-methane hydrocar-bons without the formation of coke at high temperatures of up to 900 ºC.

  9. Dissolution Behavior of Rhodium in the Na2O-SiO2 and CaO-SiO2 Slags

    Science.gov (United States)

    Wiraseranee, Chompunoot; Okabe, Toru H.; Morita, Kazuki

    2013-06-01

    To understand the behavior of rhodium during its recovery process, the dissolution behaviors of rhodium in Na2O-SiO2 and in CaO-SiO2 slags at temperatures ranging from 1423 K to 1623 K (from 1150 °C to 1350 °C) and from 1773 K to 1873 K (from 1500 °C to 1600 °C), respectively, in an oxidizing atmosphere were investigated. The solubility of rhodium in the slags was found to increase with increasing oxygen partial pressure, temperature, and the basic oxide content. The correlation between the solubility of rhodium and the oxygen partial pressure suggested that rhodium dissolved into the slags as RhO1.5. The dissolution of rhodium was slightly endothermic: the enthalpy change of the dissolution of solid rhodium was determined to be 50 ± 10 kJ/mol for the 50(mass pct)Na2O-50SiO2; and 188 ± 94 kJ/mol for the 56(mass pct)CaO-44SiO2 slag systems. The increase in the solubility of rhodium with the basic oxide content indicated that rhodium exhibits acidic behavior in slags. The correlation between the solubility of rhodium and the sulfide capacity of the slags suggested that the ionic species of rhodium in slags is the rhodate ion, RhO{2/-}. The rhodate capacity of the slags was defined, and its application to estimate the possible rhodium content in various slag systems was proposed.

  10. Single-Component Conductors: A Sturdy Electronic Structure Generated by Bulky Substituents.

    Science.gov (United States)

    Filatre-Furcate, Agathe; Bellec, Nathalie; Jeannin, Olivier; Auban-Senzier, Pascale; Fourmigué, Marc; Íñiguez, Jorge; Canadell, Enric; Brière, Benjamin; Ta Phuoc, Vinh; Lorcy, Dominique

    2016-06-20

    While the introduction of large, bulky substituents such as tert-butyl, -SiMe3, or -Si(isopropyl)3 has been used recently to control the solid state structures and charge mobility of organic semiconductors, this crystal engineering strategy is usually avoided in molecular metals where a maximized overlap is sought. In order to investigate such steric effects in single component conductors, the ethyl group of the known [Au(Et-thiazdt)2] radical complex has been replaced by an isopropyl one to give a novel single component molecular conductor denoted [Au(iPr-thiazdt)2] (iPr-thiazdt: N-isopropyl-1,3-thiazoline-2-thione-4,5-dithiolate). It exhibits a very original stacked structure of crisscross molecules interacting laterally to give a truly three-dimensional network. This system is weakly conducting at ambient pressure (5 S·cm(-1)), and both transport and optical measurements evidence a slowly decreasing energy gap under applied pressure with a regime change around 1.5 GPa. In contrast with other conducting systems amenable to a metallic state under physical or chemical pressure, the Mott insulating state is stable here up to 4 GPa, a consequence of its peculiar electronic structure. PMID:27266960

  11. Crystal structure of Δ-[Ru(bpy)2dppz]2+ bound to mismatched DNA reveals side-by-side metalloinsertion and intercalation

    Science.gov (United States)

    Song, Hang; Kaiser, Jens T.; Barton, Jacqueline K.

    2012-08-01

    DNA mismatches represent a novel target in the development of diagnostics and therapeutics for cancer, because deficiencies in DNA mismatch repair are implicated in cancers, and cells that are repair-deficient show a high frequency of mismatches. Metal complexes with bulky intercalating ligands serve as probes for DNA mismatches. Here, we report the high-resolution (0.92 Å) crystal structure of the ruthenium ‘light switch’ complex Δ-[Ru(bpy)2dppz]2+ (bpy = 2,2‧-bipyridine and dppz = dipyridophenazine), which is known to show luminescence on binding to duplex DNA, bound to both mismatched and well-matched sites in the oligonucleotide 5‧-(dCGGAAATTACCG)2-3‧ (underline denotes AA mismatches). Two crystallographically independent views reveal that the complex binds mismatches through metalloinsertion, ejecting both mispaired adenosines. Additional ruthenium complexes are intercalated at well-matched sites, creating an array of complexes in the minor groove stabilized by stacking interactions between bpy ligands and extruded adenosines. This structure attests to the generality of metalloinsertion and metallointercalation as DNA binding modes.

  12. Antitumor effect of free rhodium (II) citrate and rhodium (II) citrate-loaded maghemite nanoparticles on mice bearing breast cancer: a systemic toxicity assay.

    Science.gov (United States)

    Peixoto, Raphael Cândido Apolinário; Miranda-Vilela, Ana Luisa; de Souza Filho, José; Carneiro, Marcella Lemos' Brettas; Oliveira, Ricardo G S; da Silva, Matheus Oliveira; de Souza, Aparecido R; Báo, Sônia Nair

    2015-05-01

    Breast cancer is one of the most prevalent cancer types among women. The use of magnetic fluids for specific delivery of drugs represents an attractive platform for chemotherapy. In our previous studies, it was demonstrated that maghemite nanoparticles coated with rhodium (II) citrate (Magh-Rh2Cit) induced in vitro cytotoxicity and in vivo antitumor activity, followed by intratumoral administration in breast carcinoma cells. In this study, our aim was to follow intravenous treatment to evaluate the systemic antitumor activity and toxicity induced by these formulations in Balb/c mice bearing orthotopic 4T1 breast carcinoma. Female Balb/c mice were evaluated with regard to toxicity of intravenous treatments through analyses of hemogram, serum levels of alanine aminotransferase, iron, and creatinine and liver, kidney, and lung histology. The antitumor activity of rhodium (II) citrate (Rh2Cit), Magh-Rh2Cit, and maghemite nanoparticles coated with citrate (Magh-Cit), used as control, was evaluated by tumor volume reduction, histology, and morphometric analysis. Magh-Rh2Cit and Magh-Cit promoted a significant decrease in tumor area, and no experimental groups presented hematotoxic effects or increased levels of serum ALT and creatinine. This observation was corroborated by the histopathological examination of the liver and kidney of mice. Furthermore, the presence of nanoparticles was verified in lung tissue with no morphological changes, supporting the idea that our nanoformulations did not induce toxicity effects. No studies about the systemic action of rhodium (II) citrate-loaded maghemite nanoparticles have been carried out, making this report a suitable starting point for exploring the therapeutic potential of these compounds in treating breast cancer.

  13. Enantioselective rhodium/ruthenium photoredox catalysis en route to chiral 1,2-aminoalcohols.

    Science.gov (United States)

    Ma, Jiajia; Harms, Klaus; Meggers, Eric

    2016-08-01

    A rhodium-based chiral Lewis acid catalyst combined with [Ru(bpy)3](PF6)2 as a photoredox sensitizer allows for the visible-light-activated redox coupling of α-silylamines with 2-acyl imidazoles to afford, after desilylation, 1,2-amino-alcohols in yields of 69-88% and with high enantioselectivity (54-99% ee). The reaction is proposed to proceed via an electron exchange between the α-silylamine (electron donor) and the rhodium-chelated 2-acyl imidazole (electron acceptor), followed by a stereocontrolled radical-radical reaction. Substrate scope and control experiments reveal that the trimethylsilyl group plays a crucial role in this reductive umpolung of the carbonyl group. PMID:27462824

  14. Spectroscopic, Thermal and Biological Studies on Some Trivalent Ruthenium and Rhodium NS Chelating Thiosemicarbazone Complexes

    Directory of Open Access Journals (Sweden)

    Vinod K. Sharma

    2007-03-01

    Full Text Available The synthetic, spectroscopic, and biological studies of sixteen ring-substituted 4-phenylthiosemicarbazones and 4-nitrophenyl-thiosemicarbazones of anisaldehyde, 4-chlorobenzaldehyde, 4-fluorobenzaldehyde, and vanillin with ruthenium(III and rhodium(III chlorides are reported here. Their structures were determined on the basis of the elemental analyses, spectroscopic data (IR, electronic, H1 and C13 NMR along with magnetic susceptibility measurements, molar conductivity and thermogravimetric analyses. Electrical conductance measurement revealed a 1:3 electrolytic nature of the complexes. The resulting colored products are monomeric in nature. On the basis of the above studies, three ligands were suggested to be coordinated to each metal atom by thione sulphur and azomethine nitrogen to form low-spin octahedral complexes with ruthenium(III while forming diamagnetic complexes with rhodium(III. Both ligands and their complexes have been screened for their bactericidal activities and the results indicate that they exhibit a significant activity.

  15. Modular construction of a porous organometallic network based on rhodium olefin complexation.

    Science.gov (United States)

    Stoeck, Ulrich; Nickerl, Georg; Burkhardt, Ulrich; Senkovska, Irena; Kaskel, Stefan

    2012-10-24

    We describe the rational design and synthesis of the first member of a new class of microporous materials. It is built from rhodium and a polyolefinic ligand featuring a rigid tetraphenylsilane backbone via metal olefin complexation, creating a truly organometallic network. The resulting framework, denoted as DUT-37 (Dresden University of Technology no. 37) exhibits considerable porosity and unprecedented stability under ambient conditions. Furthermore, it is catalytically active in transfer hydrogenation.

  16. Atomic absorbtion spectrometric determination of platinum, palladium and rhodium in catalysts for automotive exhaust

    International Nuclear Information System (INIS)

    Analytical parameters of the electrothermal atomic absorption spectrometry method have been optimized for determination of platinum, palladium and rhodium in ceramic-supported catalysts for automobile exhaust gas treatment. Two chemical sample preparation methods have been proposed. In order to simplify the sample preparation procedure and to prevent the possible losses of platinum group metals the treatment of the previously ground sample with a mixture of mineral acids is recommended. (authors)

  17. Spectroscopic, Thermal and Biological Studies on Some Trivalent Ruthenium and Rhodium NS Chelating Thiosemicarbazone Complexes

    OpenAIRE

    Vinod K Sharma; Shipra Srivastava; Ankita Srivastava

    2007-01-01

    The synthetic, spectroscopic, and biological studies of sixteen ring-substituted 4-phenylthiosemicarbazones and 4-nitrophenyl-thiosemicarbazones of anisaldehyde, 4-chlorobenzaldehyde, 4-fluorobenzaldehyde, and vanillin with ruthenium(III) and rhodium(III) chlorides are reported here. Their structures were determined on the basis of the elemental analyses, spectroscopic data (IR, electronic, 1H and 13C NMR) along with magnetic susceptibility measurements, molar conductivity and thermogravimetr...

  18. Examining Rhodium Catalyst complexes for Use with Conducting Polymers Designed for Fuel Cells in Preparing Biosensors

    Energy Technology Data Exchange (ETDEWEB)

    Carpio, M.M.; Kerr, J.B.

    2005-01-01

    Biosensing devices are important because they can detect, record, and transmit information regarding the presence of, or physiological changes in, different chemical or biological materials in the environment. The goal of this research is to prepare a biosensing device that is effective, quick, and low cost. This is done by examining which chemicals will work best when placed in a biosensor. The first study involved experimenting on a rhodium catalyst complexed with ligands such as bipyridine and imidazole. The rhodium catalyst is important because it is reduced from RhIII to RhI, forms a hydride by reaction with water and releases the hydride to react with nicotinamide adenine dinucleotide (NAD+) to selectively produce 1,4-NADH, the reduced form of NAD+. The second study looked at different types of ketones and enzymes for the enzyme-substrate reaction converting a ketone into an alcohol. Preliminary results showed that the rhodium complexed with bipyridine was able to carry out all the reactions, while the rhodium complexed with imidazole was not able to produce and release hydrides. In addition, the most effective ketone to use is benzylacetone with the enzyme alcohol dehydrogenase from baker’s yeast. Future work includes experimenting with bis-imidazole, which mimics the structure of bipyridine to see if it has the capability to reduce and if the reduction rate is comparable to the bipyridine complex. Once all testing is completed, the fastest catalysts will be combined with polymer membranes designed for fuel cells to prepare biosensing devices that can be used in a variety of applications including ones in the medical and environmental fields.

  19. Tracking the shape-dependent sintering of platinum–rhodium model catalysts under operando conditions

    OpenAIRE

    Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

    2016-01-01

    Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum–rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction...

  20. Measurement of solubilities for rhodium complexes and phosphine ligands in supercritical carbon dioxide

    OpenAIRE

    Shimoyama, Yusuke; Sonoda, Masanori; Miyazaki, Kaoru; Higashi, Hidenori; Iwai, Yoshio; ARAI, Yasuhiko

    2008-01-01

    The solubilities of phosphine ligands and rhodium (Rh) complexes in supercritical carbon dioxide were measured with Fourier transform infrared (FT-IR) spectroscopy at 320 and 333 K and several pressures. Triphenylphosphine (TPP) and tris(p-trifluoromethylphenyl)-phosphine (TTFMPP) were selected as ligands for the Rh complex. The solubilities of the fluorinated ligands and complexes were compared with those of the non-fluorinated compounds. The solubilities of ligand increased up to 10 times b...

  1. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene.

    Science.gov (United States)

    Xu, Songchen; Boschen, Jeffery S; Biswas, Abhranil; Kobayashi, Takeshi; Pruski, Marek; Windus, Theresa L; Sadow, Aaron D

    2015-09-28

    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ(3)-N,Si,C-PhB(Ox(Me2))(Ox(Me2)SiHPh)Im(Mes)}Rh(H)CO][HB(C6F5)3] (, Ox(Me2) = 4,4-dimethyl-2-oxazoline; Im(Mes) = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(Ox(Me2))2Im(Mes)}RhH(SiH2Ph)CO () and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(Ox(Me2))2Im(Mes)}RhH(SiHPh)CO][HB(C6F5)3] generated by H abstraction. Complex catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C6F5)3 catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH3 as the reducing agent. PMID:26278517

  2. Synthesis and Olfactory Evaluation of Bulky Moiety-Modified Analogues to the Sandalwood Odorant Polysantol®

    Directory of Open Access Journals (Sweden)

    Adolfo Sánchez

    2009-07-01

    Full Text Available Five new bulky moiety-modified analogues of the sandalwood odorant Polysantol® have been synthesized by aldol condensation of appropriate aldehydes with butanone, deconjugative α-methylation of the resulting α,β-unsaturated ketones, and reduction of the corresponding β,γ-unsaturated ketones. The final compounds were evaluated organoleptically and one of them seemed to be of special interest for its natural sandalwood scent.

  3. Rhodium SPND's Error Reduction using Extended Kalman Filter combined with Time Dependent Neutron Diffusion Equation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jeong Hun; Park, Tong Kyu; Jeon, Seong Su [FNC Technology Co., Ltd., Yongin (Korea, Republic of)

    2014-05-15

    The Rhodium SPND is accurate in steady-state conditions but responds slowly to changes in neutron flux. The slow response time of Rhodium SPND precludes its direct use for control and protection purposes specially when nuclear power plant is used for load following. To shorten the response time of Rhodium SPND, there were some acceleration methods but they could not reflect neutron flux distribution in reactor core. On the other hands, some methods for core power distribution monitoring could not consider the slow response time of Rhodium SPND and noise effect. In this paper, time dependent neutron diffusion equation is directly used to estimate reactor power distribution and extended Kalman filter method is used to correct neutron flux with Rhodium SPND's and to shorten the response time of them. Extended Kalman filter is effective tool to reduce measurement error of Rhodium SPND's and even simple FDM to solve time dependent neutron diffusion equation can be an effective measure. This method reduces random errors of detectors and can follow reactor power level without cross-section change. It means monitoring system may not calculate cross-section at every time steps and computing time will be shorten. To minimize delay of Rhodium SPND's conversion function h should be evaluated in next study. Neutron and Rh-103 reaction has several decay chains and half-lives over 40 seconds causing delay of detection. Time dependent neutron diffusion equation will be combined with decay chains. Power level and distribution change corresponding movement of control rod will be tested with more complicated reference code as well as xenon effect. With these efforts, final result is expected to be used as a powerful monitoring tool of nuclear reactor core.

  4. Rhodium SPND's Error Reduction using Extended Kalman Filter combined with Time Dependent Neutron Diffusion Equation

    International Nuclear Information System (INIS)

    The Rhodium SPND is accurate in steady-state conditions but responds slowly to changes in neutron flux. The slow response time of Rhodium SPND precludes its direct use for control and protection purposes specially when nuclear power plant is used for load following. To shorten the response time of Rhodium SPND, there were some acceleration methods but they could not reflect neutron flux distribution in reactor core. On the other hands, some methods for core power distribution monitoring could not consider the slow response time of Rhodium SPND and noise effect. In this paper, time dependent neutron diffusion equation is directly used to estimate reactor power distribution and extended Kalman filter method is used to correct neutron flux with Rhodium SPND's and to shorten the response time of them. Extended Kalman filter is effective tool to reduce measurement error of Rhodium SPND's and even simple FDM to solve time dependent neutron diffusion equation can be an effective measure. This method reduces random errors of detectors and can follow reactor power level without cross-section change. It means monitoring system may not calculate cross-section at every time steps and computing time will be shorten. To minimize delay of Rhodium SPND's conversion function h should be evaluated in next study. Neutron and Rh-103 reaction has several decay chains and half-lives over 40 seconds causing delay of detection. Time dependent neutron diffusion equation will be combined with decay chains. Power level and distribution change corresponding movement of control rod will be tested with more complicated reference code as well as xenon effect. With these efforts, final result is expected to be used as a powerful monitoring tool of nuclear reactor core

  5. The preliminary feasibility of intercalated graphite railgun armatures

    Science.gov (United States)

    Gaier, James R.; Gooden, Clarence E.; Yashan, Doreen; Naud, Steve

    1991-01-01

    Graphite intercalation compounds may provide an excellent material for the fabrication of electromagnetic railgun armatures. As a pulse of power is fed into the armature the intercalate could be excited into the plasma state around the edges of the armature, while the bulk of the current would be carried through the graphite block. Such an armature would have both diffuse plasma armatures and bulk conduction armatures. In addition, the highly anisotropic nature of these materials could enable the electrical and thermal conductivity to be tailored to meet the specific requirements of electromagnetic railgun armatures. Preliminary investigations have been performed in an attempt to determine the feasibility of using graphite intercalation compounds as railgun armatures. Issues of fabrication, resistivity, stability, and electrical current spreading have been addressed for the case of highly oriented pyrolytic graphite.

  6. Electrochemical synthesis of alkali-intercalated iron selenide superconductors

    Science.gov (United States)

    Shen, Shi-Jie; Ying, Tian-Ping; Wang, Gang; Jin, Shi-Feng; Zhang, Han; Lin, Zhi-Ping; Chen, Xiao-Long

    2015-11-01

    Electrochemical method has been used to insert K/Na into FeSe lattice to prepare alkali-intercalated iron selenides at room temperature. Magnetization measurement reveals that KxFe2Se2 and NaxFe2Se2 are superconductive at 31 K and 46 K, respectively. This is the first successful report of obtaining metal-intercalated FeSe-based high-temperature superconductors using electrochemical method. It provides an effective route to synthesize metal-intercalated layered compounds for new superconductor exploration. Project supported by the National Natural Science Foundation of China (Grant Nos. 51322211and 91422303), the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (Grant No. XDB07020100), Beijing Nova Program of China (Grant No. 2011096), and K. C. Wong Education Foundation, Hong Kong, China.

  7. Studies in the capacitance properties of diaminoalkane-intercalated graphene

    International Nuclear Information System (INIS)

    A series of diaminoalkane-intercalated graphenes (DIGs) are successfully synthesized by intercalating graphite oxide with diaminoalkanes, followed by a reduction process using hydrazine as a reductant at room temperature. The as-prepared intercalated graphite oxides (DIGOs) and their reduced products are characterized using a variety of approaches such as X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy and elemental analysis. Electrochemical tests show that the specific capacitances of DIGOs and DIGs decrease with the increase of the interlayer distance, and that the DIGs possess larger capacitance than DIGOs after hydrazine reduction. The ion diffusion in the DIGOs/DIGs follows pseudo-second-order kinetics and is dominated mainly by their pore sizes

  8. Drug-DNA intercalation: from discovery to the molecular mechanism.

    Science.gov (United States)

    Mukherjee, Arnab; Sasikala, Wilbee D

    2013-01-01

    The ability of small molecules to perturb the natural structure and dynamics of nucleic acids is intriguing and has potential applications in cancer therapeutics. Intercalation is a special binding mode where the planar aromatic moiety of a small molecule is inserted between a pair of base pairs, causing structural changes in the DNA and leading to its functional arrest. Enormous progress has been made to understand the nature of the intercalation process since its idealistic conception five decades ago. However, the biological functions were detected even earlier. In this review, we focus mainly on the acridine and anthracycline types of drugs and provide a brief overview of the development in the field through various experimental methods that led to our present understanding of the subject. Subsequently, we discuss the molecular mechanism of the intercalation process, free-energy landscapes, and kinetics that was revealed recently through detailed and rigorous computational studies.

  9. Hydrocarbon chain conformation in an intercalated surfactant monolayer and bilayer

    Indian Academy of Sciences (India)

    N V Venkataraman; S Vasudevan

    2001-10-01

    Cetyl trimethyl ammonium (CTA) ions have been confined within galleries of layered CdPS3 at two different grafting densities. Low grafting densities are obtained on direct intercalation of CTA ions into CdPS3 to give Cd0.93PS3(CTA)0.14. Intercalation occurs with a lattice expansion of 4.8 Å with the interlamellar surfactant ion lying flat forming a monolayer. Intercalation at higher grafting densities was effected by a two-step ion-exchange process to give Cd0.83PS3(CTA)0.34, with a lattice expansion of 26.5 Å. At higher grafting densities the interlamellar surfactant ions adopt a tilted bilayer structure. 13C NMR and orientation-dependent IR vibrational spectroscopy on single crystals have been used to probe the conformation and orientation of the methylene ‘tail’ of the intercalated surfactant in the two phases. In the monolayer phase, the confined methylene chain adopts an essentially all-trans conformation with most of the trans chain aligned parallel to the gallery walls. On lowering the temperature, molecular plane aligns parallel, so that the methylene chain lies flat, rigid and aligned to the confining surface. In the bilayer phase, most bonds in the methylene chain are in trans conformation. It is possible to identify specific conformational sequences containing a gauche bond, in the interior and termini of the intercalated methylene. These high energy conformers disappear on cooling leaving all fifteen methylene units of the intercalated cetyl trimethyl ammonium ion in trans conformational registry at 40 K.

  10. Design and synthesis of threading intercalators to target DNA.

    Science.gov (United States)

    Howell, Lesley A; Gulam, Rosul; Mueller, Anja; O'Connell, Maria A; Searcey, Mark

    2010-12-01

    Threading intercalators are high affinity DNA binding agents that bind by inserting a chromophore into the duplex and locating one group in each groove. The first threading intercalators that can be conjugated to acids, sulfonic acids and peptides to target them to duplex DNA are described, based upon the well studied acridine-3- or 4-carboxamides. Cellular uptake of the parent acridine is rapid and it can be visualized in the nucleus of cells. Both the parent compounds and their conjugates maintain antitumor activity.

  11. Modification of Nanocomposites by Melting Intercalation of Polypropylene in Montmorillonite

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The polypropylene was modified by ultraviolet irradiation.The polypropylene-montmorillonite nanocomposites were prepared by direct melting intercalation of polypropylene powders.The structure of polypropylene,the polyproprlene irradiated, montmorillinote and polypropylene-montmorillonite composites were studied by XRD, IR and DSC. The results show that the PP molecules can are oxidized during ultraviolet irradiation,melt polypropylene can intercalate into montmorillonite layer.As a result,the layered distance (d001) of montmorillonite increases, and the melt absorption peak of polypropylene in layer is eliminated.

  12. Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique

    Science.gov (United States)

    Kassem, Mohammed A.; Amin, Alaa S.

    2015-02-01

    A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4‧-nitro-2‧,6‧-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50 °C, the surfactant-rich phase was heated again at 100 °C to remove water after decantation and the remaining phase was dissolved using 0.5 mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75 ng mL-1 and the detection limit was 0.15 ng mL-1 of the original solution. The enhancement factor of 500 was achieved for 250 mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples.

  13. Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique.

    Science.gov (United States)

    Kassem, Mohammed A; Amin, Alaa S

    2015-02-01

    A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4'-nitro-2',6'-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50°C, the surfactant-rich phase was heated again at 100°C to remove water after decantation and the remaining phase was dissolved using 0.5mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75ngmL(-1) and the detection limit was 0.15ngmL(-1) of the original solution. The enhancement factor of 500 was achieved for 250mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples.

  14. Lithium intercalation/de-intercalation behavior of a composite Sn/C thin film fabricated by magnetron sputtering

    Institute of Scientific and Technical Information of China (English)

    ZHAO Lingzhi; HU Shejun; LI Weishan; LI Liming; HOU Xianhua

    2008-01-01

    A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of~50 nm in thickness on it were fabricated by magnetron sputtering.The surface morphology,composition,surface distributions of alloy elements,and lithium intercalation/de-intercalation behaviors of the fabricated films were characterized by X-ray diffraction (XRD),scanning electron microscopy (SEM),electron probe microanalyzer (EPMA),X-ray photoelectron spectroscopy (XPS),inductively coupled plasma atomic emission spectrometry (ICP),cyclic voltammetry (CV),and galvanostatic charge/discharge (GC) measurements.It is found that the lithium intercalation/de-intercalation behavior of the Sn film can be significantly improved by its composite with graphite.With cycling,the discharge capacity of the Sn film without composite changes from 570 mAh/g of the 2nd cycle to 270 mAh/g of the 20th cycle,and its efficiency for the discharge and charge is between 90% and 95%.Nevertheless,the discharge capacity of the composite Sn/C film changes from 575 mAh/g of the 2nd cycle to 515 mAh/g of the 20th cycle,and its efficiency for the discharge and charge is between 95% and 100%.The performance improvement of tin by its composite with graphite is ascribed to the retardation of the bulk fin cracking from volume change during lithium intercalation and de-intercalation,which leads to the pulverization of fin.

  15. A treatment planning approach to spatially fractionated megavoltage grid therapy for bulky lung cancer

    Energy Technology Data Exchange (ETDEWEB)

    Costlow, Heather N. [Department of Radiation Oncology, Indiana University School of Medicine, Indianapolis, IN (United States); Zhang, Hualin, E-mail: hzhang@nmh.org [Department of Radiation Oncology, Indiana University School of Medicine, Indianapolis, IN (United States); Department of Radiation Oncology, Northwestern University Feinberg School of Medicine, Northwestern University, Northwestern Memorial Hospital, Chicago, IL (United States); Das, Indra J. [Department of Radiation Oncology, Indiana University School of Medicine, Indianapolis, IN (United States)

    2014-10-01

    The purpose of this study was to explore the treatment planning methods of spatially fractionated megavoltage grid therapy for treating bulky lung tumors using multileaf collimator (MLC). A total of 5 patients with lung cancer who had gross tumor volumes ranging from 277 to 635 cm{sup 3} were retrospectively chosen for this study. The tumors were from 6.5 to 9.6 cm at shortest dimension. Several techniques using either electronic compensation or intensity-modulated radiation therapy (IMRT) were used to create a variety of grid therapy plans on the Eclipse treatment planning system. The dose prescription point was calculated to the volume, and a dose of 20 Gy with 6-MV/15-MV beams was used in each plan. The dose-volume histogram (DVH) curves were obtained to evaluate dosimetric characteristics. In addition, DVH curves from a commercially available cerrobend grid collimator were also used for comparison. The linear-quadratic radiobiological response model was used to assess therapeutic ratios (TRs) and equivalent uniform doses (EUD) for all generated plans. A total of 6 different grid therapy plans were created for each patient. Overall, 4 plans had different electronic compensation techniques: Ecomps-Tubes, Ecomps-Circles, Ecomps-Squares, and Ecomps-Weave; the other 2 plans used IMRT and IMRT-Weave techniques. The DVH curves and TRs demonstrated that these MLC-based grid therapy plans can achieve dosimetric properties very similar to those of the cerrobend grid collimator. However, the MLC-based plans have larger EUDs than those with the cerrobend grid collimator. In addition, the field shaping can be performed for targets of any shape in MLC-based plans. Thus, they can deliver a more conformal dose to the targets and spare normal structures better than the cerrobend grid collimator can. The plans generated by the MLC technique demonstrated the advantage over the standard cerrobend grid collimator on accommodating targets and sparing normal structures. Overall, 6

  16. Bulky DNA Adducts in Cord Blood, Maternal Fruit-and-Vegetable Consumption, and Birth Weight in a European Mother–Child Study (NewGeneris)

    OpenAIRE

    Pedersen, Marie; Schoket, Bernadette; Godschalk, Roger W.; Wright, John; von Stedingk, Hans; Törnqvist, Margareta; Sunyer, Jordi; Nielsen, Jeanette K.; Merlo, Domenico Franco; Mendez, Michelle A.; Meltzer, Helle Margrete; Lukacs, Viktoria; Landström, Anette; Kyrtopoulos, Soterios A; Kovacs, Katalin

    2013-01-01

    Background: Tobacco-smoke, airborne, and dietary exposures to polycyclic aromatic hydrocarbons (PAHs) have been associated with reduced prenatal growth. Evidence from biomarker-based studies of low-exposed populations is limited. Bulky DNA adducts in cord blood reflect the prenatal effective dose to several genotoxic agents including PAHs. Objectives: We estimated the association between bulky DNA adduct levels and birth weight in a multicenter study and examined modification of this associat...

  17. Intercalation of paracetamol into the hydrotalcite-like host

    Science.gov (United States)

    Kovanda, František; Maryšková, Zuzana; Kovář, Petr

    2011-12-01

    Hydrotalcite-like compounds are often used as host structures for intercalation of various anionic species. The product intercalated with the nonionic, water-soluble pharmaceuticals paracetamol, N-(4-hydroxyphenyl)acetamide, was prepared by rehydration of the Mg-Al mixed oxide obtained by calcination of hydrotalcite-like precursor at 500 °C. The successful intercalation of paracetamol molecules into the interlayer space was confirmed by powder X-ray diffraction and infrared spectroscopy measurements. Molecular simulations showed that the phenolic hydroxyl groups of paracetamol interact with hydroxide sheets of the host via the hydroxyl groups of the positively charged sites of Al-containing octahedra; the interlayer water molecules are located mostly near the hydroxide sheets. The arrangement of paracetamol molecules in the interlayer is rather disordered and interactions between neighboring molecules cause their tilting towards the hydroxide sheets. Dissolution tests in various media showed slower release of paracetamol intercalated in the hydrotalcite-like host in comparison with tablets containing the powdered pharmaceuticals.

  18. Intercalation of papain enzyme into hydrotalcite type layered double hydroxide

    Science.gov (United States)

    Zou, N.; Plank, J.

    2012-09-01

    Intercalation of proteolytic enzyme papain into hydrotalcite type LDH structure was achieved by controlled co-precipitation at pH=9.0 in the presence of papain. Characterization of the MgAl-papain-LDH phase was carried out using X-ray powder diffraction (XRD), elemental analysis, infrared spectroscopy (IR) and thermogravimetry (TG). According to XRD, papain was successfully intercalated. The d-value for the basal spacing of MgAl-papain-LDH was found at ˜5.3 nm. Consequently, original papain (hydrodynamic diameter ˜7.2 nm) attains a compressed conformation during intercalation.Formation of MgAl-papain-LDH was confirmed by elemental analysis and transmission electron microscopy (TEM). Under SEM, MgAl-papain-LDH phases appear as nanothin platelets which are intergrown to flower-like aggregates. Steric size and activity of the enzyme was retained after deintercalation from MgAl-LDH framework, as was evidenced by light scattering and UV/vis measurements. Thus, papain is not denatured during intercalation, and LDH is a suitable host structure which can provide a time-controlled release of the biomolecule.

  19. Enantiospecific kinking of DNA by a partially intercalating metal complex

    KAUST Repository

    Reymer, Anna

    2012-01-01

    Opposite enantiomers of [Ru(phenanthroline) 3] 2+ affect the persistence length of DNA differently, a long speculated effect of helix kinking. Our molecular dynamics simulations confirm a substantial change of duplex secondary structure produced by wedge-intercalation of one but not the other enantiomer. This effect is exploited by several classes of DNA operative proteins. © The Royal Society of Chemistry 2012.

  20. Capacitive Sensing of Intercalated H2O Molecules Using Graphene.

    Science.gov (United States)

    Olson, Eric J; Ma, Rui; Sun, Tao; Ebrish, Mona A; Haratipour, Nazila; Min, Kyoungmin; Aluru, Narayana R; Koester, Steven J

    2015-11-25

    Understanding the interactions of ambient molecules with graphene and adjacent dielectrics is of fundamental importance for a range of graphene-based devices, particularly sensors, where such interactions could influence the operation of the device. It is well-known that water can be trapped underneath graphene and its host substrate; however, the electrical effect of water beneath graphene and the dynamics of how the interfacial water changes with different ambient conditions has not been quantified. Here, using a metal-oxide-graphene variable-capacitor (varactor) structure, we show that graphene can be used to capacitively sense the intercalation of water between graphene and HfO2 and that this process is reversible on a fast time scale. Atomic force microscopy is used to confirm the intercalation and quantify the displacement of graphene as a function of humidity. Density functional theory simulations are used to quantify the displacement of graphene induced by intercalated water and also explain the observed Dirac point shifts as being due to the combined effect of water and oxygen on the carrier concentration in the graphene. Finally, molecular dynamics simulations indicate that a likely mechanism for the intercalation involves adsorption and lateral diffusion of water molecules beneath the graphene. PMID:26502269

  1. [Raman and infrared spectrograms of organic borate intercalated hydrotalcite].

    Science.gov (United States)

    Zhang, Jing-Yu; Bai, Zhi-Min; Zhao, Dong

    2013-03-01

    The pattern of X-ray diffraction, the Raman and infrared spectra of organic borate intercalated hydrotalcite were discussed. The well crystallized zinc-aluminum layered double hydroxides (Zn-Al LDHs) intercalated by carbonate ions and borate ions were respectively prepared by co-precipitation method. Patterns of X-ray diffraction showed that the (003) reflection of borate-LDHs was sharp and symmetric and shifted to lower angle than that of carbonate-LDHs. The gallery height of borate-LDHs increased from 0. 28 nm to 0.42 nm after intercalation, indicating that interlayered carbonate ions were substituted by borate anions. The Raman and IR spectra showed that specific bands of carbonate ions in the borate-LDHs disappeared, but with the presence of B3O3(OH)4- X B4O5(OH)4(2-) and B(OH)4- in the interlayer galleries. The hydroxide interlayer anions had a significant influence on the band positions in Raman and infrared spectra of modes related to the hydroxyl group. Our results indicate that single phase and pure borate-pillared LDHs can be obtained using tributyl orthoborate as intercalating agents, and the change in the structure and nature of hydrotalcite can be detected precisely by Raman spectroscopy. PMID:23705437

  2. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance.

    Science.gov (United States)

    Augustyn, Veronica; Come, Jérémy; Lowe, Michael A; Kim, Jong Woung; Taberna, Pierre-Louis; Tolbert, Sarah H; Abruña, Héctor D; Simon, Patrice; Dunn, Bruce

    2013-06-01

    Pseudocapacitance is commonly associated with surface or near-surface reversible redox reactions, as observed with RuO2·xH2O in an acidic electrolyte. However, we recently demonstrated that a pseudocapacitive mechanism occurs when lithium ions are inserted into mesoporous and nanocrystal films of orthorhombic Nb2O5 (T-Nb2O5; refs 1,2). Here, we quantify the kinetics of charge storage in T-Nb2O5: currents that vary inversely with time, charge-storage capacity that is mostly independent of rate, and redox peaks that exhibit small voltage offsets even at high rates. We also define the structural characteristics necessary for this process, termed intercalation pseudocapacitance, which are a crystalline network that offers two-dimensional transport pathways and little structural change on intercalation. The principal benefit realized from intercalation pseudocapacitance is that high levels of charge storage are achieved within short periods of time because there are no limitations from solid-state diffusion. Thick electrodes (up to 40 μm thick) prepared with T-Nb2O5 offer the promise of exploiting intercalation pseudocapacitance to obtain high-rate charge-storage devices.

  3. Methotrexate intercalated ZnAl-layered double hydroxide

    International Nuclear Information System (INIS)

    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 A in pristine LDH to 21.3 A 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. - Graphical abstract: ZnAl-layered double hydroxide intercalated with methotrexate (∼34% loading) promises the possibility of use of ZnAl-LDH material as drug carrier and in controlled delivery. Highlights: → ZnAl-layered double hydroxide methotrexate nanohybrid has been synthesized. → XRD and TEM studies on nanohybrid revealed successful intercalation of methotrexate. → TG and CHN analyses showed ∼34 wt% of methotrexate loading into the nanohybrid. → Possibility of use of ZnAl-LDH material as drug carrier and in delivery.

  4. Intercalation, DNA Kinking, and the Control of Transcription

    Science.gov (United States)

    Werner, Milton H.; Gronenborn, Angela M.; Marius Clore, G.

    1996-02-01

    Biological processes involved in the control and regulation of transcription are dependent on protein-induced distortions in DNA structure that enhance the recruitment of proteins to their specific DNA targets. This function is often accomplished by accessory factors that bind sequence specifically and locally bend or kink the DNA. The recent determination of the three-dimensional structures of several protein-DNA complexes, involving proteins that perform such architectural tasks, brings to light a common theme of side chain intercalation as a mechanism capable of driving the deformation of the DNA helix. The protein scaffolds orienting the intercalating side chain (or side chains) are structurally diverse, presently comprising four distinct topologies that can accomplish the same task. The intercalating side chain (or side chains), however, is exclusively hydrophobic. Intercalation can either kink or bend the DNA, unstacking one or more adjacent base pairs and locally unwinding the DNA over as much as a full turn of helix. Despite these distortions, the return to B-DNA helical parameters generally occurs within the adjacent half-turns of DNA.

  5. Electret effect in intercalated crystals of the AIIIBVI group

    Directory of Open Access Journals (Sweden)

    I.Grygorchak

    2007-01-01

    Full Text Available Measurements of dielectric properties of Ni-intercalated GaSe and InSe have been performed. The present study is aimed at the investigation of the low-admixture region where the intercalation induced electret effect occurs. The effect exhibits pronounced peak-like concentration dependences and a non-monotonous temperature behaviour with maximum magnitudes at low temperatures. Intercalation leads to over tenfold increase of dielectric permittivity over the whole measured frequency range with up to several orders at low frequencies for GaSe. Temperature dependences of the permittivity demonstrate well-defined peaks with localizations and heights strongly depending on the concentration. A microscopic model of order-disorder type has been proposed that considers redistribution of intercalant atoms between non-polar octahedral and polar tetrahedral positions in the crystal van der Waals gaps. Such a redistribution can occur in the form of phase transition to the polar phase (corresponding to the electret effect which is stabilized by the internal field. For the case of octahedral positions being more preferable, the model predicts a peak-like dependence of the crystal polarization on chemical potential due to passing through the interjacent polar phase in accordance with the measured behaviour of the electret effect. The calculated temperature dependences of dielectric susceptibility qualitatively reproduce experimental results for permittivity as well.

  6. Exfoliation of Hexagonal Boron Nitride via Ferric Chloride Intercalation

    Science.gov (United States)

    Hung, Ching-cheh; Hurst, Janet; Santiago, Diana; Rogers, Richard B.

    2014-01-01

    Sodium fluoride (NaF) was used as an activation agent to successfully intercalate ferric chloride (FeCl3) into hexagonal boron nitride (hBN). This reaction caused the hBN mass to increase by approx.100 percent, the lattice parameter c to decrease from 6.6585 to between 6.6565 and 6.6569 ?, the x-ray diffraction (XRD) (002) peak to widen from 0.01deg to 0.05deg of the full width half maximum value, the Fourier transform infrared (FTIR) spectrum's broad band (1277/cm peak) to change shape, and new FTIR bands to emerge at 3700 to 2700 and 1600/cm. This indicates hBN's structural and chemical properties are significantly changed. The intercalated product was hygroscopic and interacted with moisture in the air to cause further structural and chemical changes (from XRD and FTIR). During a 24-h hold at room temperature in air with 100 percent relative humidity, the mass increased another 141 percent. The intercalated product, hydrated or not, can be heated to 750 C in air to cause exfoliation. Exfoliation becomes significant after two intercalation-air heating cycles, when 20-nm nanosheets are commonly found. Structural and chemical changes indicated by XRD and FTIR data were nearly reversed after the product was placed in hydrochloric acid (HCl), resulting in purified, exfoliated, thin hBN products.

  7. Effect of rhodium modification on structures of sulfiede Rh-Mo-K/Al2O3 catalysts studied by XAFS

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Local structures of the molybdenum sulfide species in the sultided Rh-Mo-K/Al2O3 catalysts with various rhodium loadings have been investigated by XAFS.From the fitting results.the Mo-Mo coordination number for the sample free of rhodium(ca.3.7) is similar to that for the crystalline MoS2,indicating that the supported sulfided molybdenum species mainly present as large pateches of MoS2-like slabs.For the rhodium-modified samples,however,the amplitudes of the Mo-S and Mo-Mo coordination shells are sharply reduced,revealing a high dispersion of the MoS2-like species in the catalysts,The scheme of the microstructures of the sulfided molybdenum species stabilized on the alumina support is discussed based upon the analysis of the EXAFS data.

  8. A rhodium/silicon co-electrocatalyst design concept to surpass platinum hydrogen evolution activity at high overpotentials.

    Science.gov (United States)

    Zhu, Lili; Lin, Haiping; Li, Youyong; Liao, Fan; Lifshitz, Yeshayahu; Sheng, Minqi; Lee, Shuit-Tong; Shao, Mingwang

    2016-01-01

    Currently, platinum-based electrocatalysts show the best performance for hydrogen evolution. All hydrogen evolution reaction catalysts should however obey Sabatier's principle, that is, the adsorption energy of hydrogen to the catalyst surface should be neither too high nor too low to balance between hydrogen adsorption and desorption. To overcome the limitation of this principle, here we choose a composite (rhodium/silicon nanowire) catalyst, in which hydrogen adsorption occurs on rhodium with a large adsorption energy while hydrogen evolution occurs on silicon with a small adsorption energy. We show that the composite is stable with better hydrogen evolution activity than rhodium nanoparticles and even exceeding those of commercial platinum/carbon at high overpotentials. The results reveal that silicon plays a key role in the electrocatalysis. This work may thus open the door for the design and fabrication of electrocatalysts for high-efficiency electric energy to hydrogen energy conversion. PMID:27447292

  9. Technical Report-Final-Electrochemistry of Nanostructured Intercalation Hosts

    Energy Technology Data Exchange (ETDEWEB)

    Professor William H. Smyrl, Principal Investigator

    2009-03-09

    We have shown that: (1) Li+ ions are inserted reversibly, without diffusion control, up to the level of at least 4 moles Li+ ions per mole for V2O5, in the aerogel (ARG) form (500 m2/g specific surface area) and aerogel-like (ARG-L) form (200 m2/g specific surface area)(6,7,1,2); (2) polyvalent cations (Al+3, Mg+2, Zn+2) may be intercalated reversibly into V2O5 (ARG) with high capacity (approaching 4 equivalents/mole V2O5 (ARG)) for each (5); (3) dopant cations such as Ag+ and Cu+2 increase the conductivity of V2O5 (XRG) up to three orders of magnitude(3), they are electrochemically active – showing reduction to the metallic-state in parallel to intercalation of Li+ ions – but are not released to the electrolyte upon oxidation and Li+ ion release (Cu+2 ions are reduced to Cu metal and reoxidized to Cu+2 in Li+ ion insertion/release cycles, but the copper ions are not released to the electrolyte over more than 400 cycles of the XRG form); (4) we have shown that Cu+2 ion (dopant) and Zn+2 ions (chemical insertion and dopant) occupy the same intercalation site inV2O5 xerogel and aerogel(4); (5) the reversible intercalation of Zn+2, Mg+2, and Al+3 in the ARG(11) indicates that these cations are “mobile”, but that Cu+2 ions and Ag+ ions are “immobile” in the xerogel, i.e., the latter ions are not exchanged with the electrolyte in Li+ ion intercalation cycling(3).

  10. Modeling the effect of intercalators on the high-force stretching behavior of DNA

    CERN Document Server

    Schakenraad, Koen; Biebricher, Andreas; Wuite, Gijs; Storm, Cornelis; van der Schoot, Paul

    2015-01-01

    DNA is structurally and mechanically altered by the binding of intercalator molecules. Intercalation strongly affects the force-extension behavior of DNA, in particular the overstretching transition. We present a statistical model that captures all relevant findings of recent force-extension experiments. Two predictions from our model are presented. The first suggests the existence of a novel hyper-stretching regime in the presence of intercalators and the second, a linear dependence of the overstretching force on intercalator concentration, is verified by re-analyzing available experimental data. Our model pins down the physical principles that govern intercalated DNA mechanics, providing a predictive understanding of its limitations and possibilities.

  11. Formation Energies of the Lithium Intercalations in MoS2

    Institute of Scientific and Technical Information of China (English)

    Aiyu LI; Huiying LIU; Zizhong ZHU; Meichun HUANG; Yong YANG

    2006-01-01

    First-principles calculations have been performed to study the lithium intercalations in MoS2. The formation energies, changes of volumes, electronic structures and charge densities of the lithium intercalations in MoS2 are presented. Our calculations show that during lithium intercalations in MoS2, the lithium intercalation formation energies per lithium atom are between 2.5 eV to 3.0 eV, The volume expansions of MoS2 due to lithium intercalations are relatively small

  12. High-Density Chemical Intercalation of Zero-Valent Copper into Bi 2 Se 3 Nanoribbons

    KAUST Repository

    Koski, Kristie J.

    2012-05-09

    A major goal of intercalation chemistry is to intercalate high densities of guest species without disrupting the host lattice. Many intercalant concentrations, however, are limited by the charge of the guest species. Here we have developed a general solution-based chemical method for intercalating extraordinarily high densities of zero-valent copper metal into layered Bi 2Se 3 nanoribbons. Up to 60 atom % copper (Cu 7.5Bi 2Se 3) can be intercalated with no disruption to the host lattice using a solution disproportionation redox reaction. © 2012 American Chemical Society.

  13. Tuning the self-assembly of the bioactive dipeptide L-carnosine by incorporation of a bulky aromatic substituent

    OpenAIRE

    Castelletto, Valeria; Cheng, Ge; Greenland, Barny W.; Hamley, Ian W.; Harris, Peter J. F.

    2011-01-01

    The dipeptide L-carnosine has a number of important biological properties. Here, we explore the effect of attachment of a bulky hydrophobic aromatic unit, Fmoc [N-(fluorenyl-9-methoxycarbonyl)] on the self-assembly of Fmoc-L-carnosine, i.e., Fmoc-Beta-alanine-histidine (Fmoc-BetaAH). It is shown that Fmoc-BetaAH forms well-defined amyloid fibril containing Beta sheets above a critical aggregation concentration, which is determined from pyrene and ThT fluorescence experiments. Twisted fi...

  14. Unexpected binding orientation of bulky-B-ring anti-androgens and implications for future drug targets.

    Science.gov (United States)

    Duke, Charles B; Jones, Amanda; Bohl, Casey E; Dalton, James T; Miller, Duane D

    2011-06-01

    Several new androgen receptor antagonists were synthesized and found to have varying activities across typically anti-androgen resistant mutants (Thr877 → Ala and Trp741 → Leu) and markedly improved potency over previously reported pan-antagonists. X-ray crystallography of a new anti-androgen in an androgen receptor mutant (Thr877 → Ala) shows that the receptor can accommodate the added bulk presented by phenyl to naphthyl substitution, casting doubt on previous reports of predicted binding orientation and the causes of antagonism in bulky-B-ring antagonists.

  15. Intrinsic Selectivity and Structure Sensitivity of Rhodium Catalysts for C(2+) Oxygenate Production.

    Science.gov (United States)

    Yang, Nuoya; Medford, Andrew J; Liu, Xinyan; Studt, Felix; Bligaard, Thomas; Bent, Stacey F; Nørskov, Jens K

    2016-03-23

    Synthesis gas (CO + H2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculations using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate-adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ∼6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. This work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements. PMID:26958997

  16. Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

    Energy Technology Data Exchange (ETDEWEB)

    Mauro, Marcella [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy); Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo [University of Trieste, Department of Chemical and Pharmaceutical Sciences (Italy); Jaganjac, Morana [Rudjer Boskovic Institute, Laboratory for Oxidative Stress, Department of Molecular Medicine (Croatia); Bovenzi, Massimo; Filon, Francesca Larese, E-mail: larese@units.it [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy)

    2015-06-15

    The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na{sub 2}PtC{sub l6} and RhCl{sub 3}·3H{sub 2}O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm{sup −2} h{sup −1} and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration.

  17. Preparation of a cationic azobenzene dye-montmorillonite intercalation compound and its photochemical behavior

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Montmorillonite/cationic azobenzene dye (GTL) intercalation compounds were prepared by the conventional ion exchange method. As compared with that of pure GTL, the thermal stability of the intercalated GTL was greatly enhanced, and the absorption band corresponding to azobenzene group in intercalated GTL shifted towards a longer wavelength by 55 nm, which could be ascribed to the strong conjugation of GTL supramolecular order structure (J cluster) confined in a nanoscale space of montmorillonite interlayer gallery. The microstructures of the resulting intercalation compounds could be successfully controlled by varying the amount of dye loaded as evidenced by the basal spacing of the intercalation compounds. The intercalated azo dye in the montmorillonite interlayer space exhibited reversible trans-to-cis photoisomerization and thermal cis-to-trans reaction. FTIR proved the successful intercalation of GTL into the silicate layer.

  18. Screen-Printed Carbon Electrodes Modified by Rhodium Dioxide and Glucose Dehydrogenase

    OpenAIRE

    Vojtěch Polan; Jan Soukup; Karel Vytřas

    2011-01-01

    The described glucose biosensor is based on a screen-printed carbon electrode (SPCE) modified by rhodium dioxide, which functions as a mediator. The electrode is further modified by the enzyme glucose dehydrogenase, which is immobilized on the electrode's surface through electropolymerization with m-phenylenediamine. The enzyme biosensor was optimized and tested in model glucose samples. The biosensor showed a linear range of 500–5000 mg L−1 of glucose with a detection limit of 210 mg L−1 (es...

  19. POLYMER—SUPPORTED RHODIUM CATALYSTS FOR CARBONYLATION OF METHYL ACETATE TO ACETIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    CHENDean; HUANGShizhuan; 等

    1993-01-01

    Two kinds of rhodium catalysts supported on cross-linked styrene-divinylbenzene copolymers containing bipyridine or o-phenylene diamine have been prepared and found to display high activity for methyl acetate carbonylation to form acetic anhydride,the activities are even higher than their homogeneous counterparts. XPS analysis was used to characterize the synthetic catalysts.The apparent activation parameters were determined to be Eα=73.3KJ/mol,ΔH≠=66.3KJ/mol,ΔS≠=-28.6eu.These parameters are very close to those in methanol carbonylation and imply to have analogous mechanism in both cases.

  20. A novel technique of in situ phase-shift interferometry applied for faint dissolution of bulky montmorillonite in alkaline solution

    International Nuclear Information System (INIS)

    The effect of alkaline pH on the dissolution rate of bulky aggregated montmorillonite samples at 23°C was investigated for the first time by using an enhanced phase-shift interferometry technique combined with an internal refraction interferometry method developed for this study. This technique was applied to provide a molecular resolution during the optical observation of the dissolution phenomena in real time and in situ while remaining noninvasive. A theoretical normal resolution limit of this technique was 0.78 nm in water for opaque material, but was limited to 6.6 nm for montmorillonite due to the transparency of the montmorillonite crystal. Normal dissolution velocities as low as 1 × 10-4 to 1 × 10-3 nm/s were obtained directly by using the measured temporal change in height of montmorillonite samples set in a reaction cell. The molar dissolution fluxes of montmorillonite obtained in this study gave considerably faster dissolution rates in comparison to those obtained in previous investigations by solution analysis methods. The pH dependence of montmorillonite dissolution rate determined in this study was qualitatively in good agreement with those reported in the previous investigations. The dissolution rates to be used in safety assessments of geological repositories for radioactive wastes should be obtained for bulky samples. This goal has been difficult to achieve using conventional powder experiment technique and solution analysis method, but has been shown to be feasible using the enhanced phase-shift interferometry. (author)

  1. EXAFS Determination of the Change in the Structure of Rhodium in Highly Dispersed Rhodium/gamma-Aluminum Oxide Catalysts after Carbon Monoxide and/or Hydrogen Adsorption at Different Temperatures

    NARCIS (Netherlands)

    Koningsberger, D.C.; Blik, H.F.J. van 't; Zon, J.B.A.D. van; Prins, R.

    1984-01-01

    Extended X-ray absorption spectroscopy (EXAFS) has been applied to study the Rh K-edge of two ultradisperse Rh/Al{2}O{3} catalysts containing 0.47 and 1.04 wt.% rhodium respectively. The structural properties of the Rh crystallites were determined after reduction with H{2}, evacuation at elevated te

  2. Controlling the photoconductivity: Graphene oxide and polyaniline self assembled intercalation

    Energy Technology Data Exchange (ETDEWEB)

    Vempati, Sesha, E-mail: svempati01@qub.ac.uk [UNAM-National Nanotechnology Research Centre, Bilkent University, Ankara 06800 (Turkey); Ozcan, Sefika [UNAM-National Nanotechnology Research Centre, Bilkent University, Ankara 06800 (Turkey); Department of Polymer Science and Technology, Middle East Technical University, Ankara 06800 (Turkey); Uyar, Tamer, E-mail: uyar@unam.bilkent.edu.tr [UNAM-National Nanotechnology Research Centre, Bilkent University, Ankara 06800 (Turkey); Institute of Materials Science and Nanotechnology, Bilkent University, Ankara 06800 (Turkey)

    2015-02-02

    We report on controlling the optoelectronic properties of self-assembled intercalating compound of graphene oxide (GO) and HCl doped polyaniline (PANI). Optical emission and X-ray diffraction studies revealed a secondary doping phenomenon of PANI with –OH and –COOH groups of GO, which essentially arbitrate the intercalation. A control on the polarity and the magnitude of the photoresponse (PR) is harnessed by manipulating the weight ratios of PANI to GO (viz., 1:1.5 and 1:2.2 are abbreviated as PG1.5 and PG2.2, respectively), where ±PR = 100(R{sub Dark} – R{sub UV-Vis})/R{sub Dark} and R corresponds to the resistance of the device in dark or UV-Vis illumination. To be precise, the PR from GO, PANI, PG1.5, and PG2.2 are +34%, −111%, −51%, and +58%, respectively.

  3. Abl suppresses cell extrusion and intercalation during epithelium folding.

    Science.gov (United States)

    Jodoin, Jeanne N; Martin, Adam C

    2016-09-15

    Tissue morphogenesis requires control over cell shape changes and rearrangements. In the Drosophila mesoderm, linked epithelial cells apically constrict, without cell extrusion or intercalation, to fold the epithelium into a tube that will then undergo epithelial-to-mesenchymal transition (EMT). Apical constriction drives tissue folding or cell extrusion in different contexts, but the mechanisms that dictate the specific outcomes are poorly understood. Using live imaging, we found that Abelson (Abl) tyrosine kinase depletion causes apically constricting cells to undergo aberrant basal cell extrusion and cell intercalation. abl depletion disrupted apical-basal polarity and adherens junction organization in mesoderm cells, suggesting that extruding cells undergo premature EMT. The polarity loss was associated with abnormal basolateral contractile actomyosin and Enabled (Ena) accumulation. Depletion of the Abl effector Enabled (Ena) in abl-depleted embryos suppressed the abl phenotype, consistent with cell extrusion resulting from misregulated ena Our work provides new insight into how Abl loss and Ena misregulation promote cell extrusion and EMT.

  4. Preparation of PAA/AM/MMT Hybrid by Intercalation Polymerization

    Institute of Scientific and Technical Information of China (English)

    WANG YunPu; HAO JinQing; XIONG YuBin; CHEN NaLi; ZHA RuiTao

    2001-01-01

    @@ Over the last few years, Montmorillonite (MMT) was widely used as a special inorganic material for preparing Polymer/MMT nanocompsites. MMT is a clay imineral consisting of stacked silicate sheets whose thickness is about 10A. Through intercalation a large number of polymer-clay nanocomposites have been prepared such as Nylon-clay hybrid [1], PS-clay hybrid [2], Poly (methyl methacrylate) (PMMA)-clay hybrid [3], etc. In this article, the synthesis and properties of Poly (acrylic acid/acrylamide)/MMT hybrid (PAAAM/MMT) were studied. X-ray diffraction and Transmission electron microscopy were used to characterize the hybrid material. DSC has been used to study its property. Results showed that the intercalating reagents have entered the space of MMT's layers and enlarged them. At the same time, the MMT dispersed homogeneously in acrylic acid and acrylamide monomers that allow MMT to disperse in PAAAM matrix in the monolayer form.

  5. Intercalation of trichloroethene by sediment-associated clay minerals.

    Science.gov (United States)

    Matthieu, D E; Brusseau, M L; Johnson, G R; Artiola, J L; Bowden, M L; Curry, J E

    2013-01-01

    The objective of this research was to examine the potential for intercalation of trichloroethene (TCE) by clay minerals associated with aquifer sediments. Sediment samples were collected from a field site in Tucson, AZ. Two widely used Montmorillonite specimen clays were employed as controls. X-ray diffraction, conducted with a controlled-environment chamber, was used to characterize smectite interlayer d-spacing for three treatments (bulk air-dry sample, sample mixed with synthetic groundwater, sample mixed with TCE-saturated synthetic groundwater). The results show that the d-spacing measured for the samples treated with TCE-saturated synthetic groundwater are larger (~26%) than those of the untreated samples for all field samples as well as the specimen clays. These results indicate that TCE was intercalated by the clay minerals, which may have contributed to the extensive elution tailing observed in prior miscible-displacement experiments conducted with this sediment.

  6. Intercalated graphite fiber composites as EMI shields in aerospace structures

    Science.gov (United States)

    Gaier, James R.

    1992-01-01

    The requirements for electromagnetic interference (EMI) shielding in aerospace structures are more complicated than those for ground structures because of their weight limitations. As a result, the best EMI shielding materials must combine low density, high strength, and high elastic modulus with high shielding ability. EMI shielding characteristics were calculated for shields formed from pristine and intercalated graphite fiber/epoxy composites and compare to preliminary experimental results for these materials and to the characteristics of shields made from aluminum. Calculations indicate that effective EMI shields could be fabricated from intercalated graphite composites which would have less than 12 percent of the mass of conventional aluminum shields, based on mechanical properties and shielding characteristics alone.

  7. Phase Separation Dynamics in Isotropic Ion-Intercalation Particles

    CERN Document Server

    Zeng, Yi

    2013-01-01

    Lithium-ion batteries exhibit complex nonlinear dynamics, resulting from diffusion and phase transformations coupled to ion intercalation reactions. Using the recently developed Cahn-Hilliard reaction (CHR) theory, we investigate a simple mathematical model of ion intercalation in a spherical solid nanoparticle, which predicts transitions from solid-solution radial diffusion to two-phase shrinking-core dynamics. This general approach extends previous Li-ion battery models, which either neglect phase separation or postulate a spherical shrinking-core phase boundary, by predicting phase separation only under appropriate circumstances. The effect of the applied current is captured by generalized Butler-Volmer kinetics, formulated in terms of diffusional chemical potentials, and the model consistently links the evolving concentration profile to the battery voltage. We examine sources of charge/discharge asymmetry, such as asymmetric charge transfer and surface "wetting" by ions within the solid, which can lead to...

  8. Induced magnetism in transition metal intercalated graphitic systems

    KAUST Repository

    Kaloni, Thaneshwor P.

    2011-10-26

    We investigate the structure, chemical bonding, electronic properties, and magnetic behavior of a three-dimensional graphitic network in aba and aaa stacking with intercalated transition metal atoms (Mn, Fe, Co, Ni, and Cu). Using density functional theory, we find induced spin-polarization of the C atoms both when the graphene sheets are aba stacked (forming graphite) and aaa stacked (resembling bi-layer graphene). The magnetic moment induced by Mn, Fe, and Co turns out to vary from 1.38 μB to 4.10 μB, whereas intercalation of Ni and Cu does not lead to a magnetic state. The selective induction of spin-polarization can be utilized in spintronic and nanoelectronic applications.

  9. Preparation of polystyrene–clay nanocomposite by solution intercalation technique

    Indian Academy of Sciences (India)

    P K Paul; S A Hussain; D Bhattacharjee; M Pal

    2013-06-01

    Polymer–clay nanocomposites of commercial polystyrene (PS) and clay laponite were prepared via solution intercalation technique. Laponite was modified suitably with the well known cationic surfactant cetyltrimethyl ammonium bromide by ion-exchange reaction to render laponite miscible with hydrophobic PS. X-ray diffraction analysis in combination with scanning electron microscopy gives an idea of structural and morphological information of PS–laponite nanocomposite for different varying organo-laponite contents. Intercalation of PS chain occurs into the interlayer spacings of laponite for low organo-laponite concentration in the PS–O-laponite mixture. However, aggregation and agglomeration occur at higher clay concentration. The molecular bond vibrational profile of laponite as well as PS–laponite nanocomposite have been explored by Fourier transform infrared spectroscopy. Thermogravimetric analysis along with differential scanning calorimetry results reveal the enhancement of both thermal stability and glass transition temperature of PS due to the incorporation of clay platelets.

  10. Synthesis of graphene oxide-intercalated alpha-hydroxides by metathesis and their decomposition to graphene/metal oxide composites

    OpenAIRE

    Nethravathi, C; Rajamathi, Michael; Ravishankar, N.; Basit, Lubna; FELSER, CLAUDIA

    2010-01-01

    Graphene oxide-intercalated alpha-metal hydroxides were prepared using layers from the delaminated colloidal dispersions of cetyltrimethylammonium-intercalated graphene oxide and dodecylsulfate-intercalated alpha-hydroxide of nickel/cobalt as precursors. The reaction of the two dispersions leads to de-intercalation of the interlayer ions from both the layered solids and the intercalation of the negatively charged graphene oxide sheets between the positively charged layers of the alpha-hydroxi...

  11. Preferential Intercalation of Pyridinedicarboxylates into Layered Double Hydroxides

    Institute of Scientific and Technical Information of China (English)

    李蕾; 莫丹; 陈大舟

    2005-01-01

    Intercalation of 2,3-,2,4-,2,5-,2,6-,3,4-,or3,5-pyridincdicarboxylate into the layered double hydroxide (LDH),[Mg0.73AIo.27(OH)2](CO3)0.14*1.34H2O was carried out by the reconstruction method in the molar ratio of organic acid: calcined LDH=3:8, in 80% alcoholic aqueous solution at 70℃. Selective reaction was observed in com-petitive experiments involving an equal concentration pairs of acids. The preference order of the organic acids intercalated into the Mg-Al-LDH was found to be in the order of 2,3-pyridinedicarboxylate>2,5-pyridinedicarboxylate>2,4-pyridinedicarboxylate>3,5-pyridinedicarboxylate>3,4-pyridinedicarboxylate>2,6-pyridinedic arboxylate. The structures of the intercalates formed by the reaction of six guests with Mg-Al-LDH were characterized by X-ray diffraction, infrared and thermogravimetry techniques. And the charge density on the oxygens of each of the carboxylate groups for the six anions was investigated utilizing ab initio (HF/6-31G) method by G98w. From the X-ray diffraction data, the guest size and the charge density of the oxygens of the guest, the orientation of 2,3-,2,4-,2,5-,2,6-,3,4-, or 3,5-pyridinedicarboxylate anions between the layers was determined and the preferential intercalation mechanism was discussed. These results indicate the possibility of a molecular recognition ability of LDH and it would be exploited for the chemical separation of some anions from solution.

  12. Curie and Pauli Spins in Lithium Intercalated MCMB

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The ESR signal of lithium intercalated MCMB can be well simulated by combination of a Lorentz curve and a Gauss curve. The ESR intensity of the Lorentz component is essentially independent of temperature while the Gauss component shows a linear change with the reciprocal of temperature, indicative of Pauli spin and Curie spin, respectively. The former is probably associated with the ordered (graphitized) structures while the latter with the disordered structures in the sample.

  13. Intercalation of Epinephrine with Calf-thymus ds-DNA

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A strong interaction between double stranded calf-thymus DNA (ds-DNA) and epinephrine but no interaction between single stranded calf-thymus DNA (ss-DNA) and epinephrine were observed by the use of UV-spectroscopy and cyclic voltammetry. It is suggested that the interaction leads to an intercalation of EP molecules into the groove of ds-DNA and the formation of ds-DNA(EP)n complex.

  14. Tracking the shape-dependent sintering of platinum-rhodium model catalysts under operando conditions

    Science.gov (United States)

    Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

    2016-03-01

    Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum-rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio.

  15. Signal anticipation of rhodium self powered neutron detectors for on-line applications

    International Nuclear Information System (INIS)

    Rhodium self powered neutron detectors (SPND) have been used for a long time in the experimental devices at the SILOE reactor. In a time-dependent neutron flux, the rhodium SPND behaves as a first order linear system. Consequently, the response of the SPND is not similar to the incident flux evolution because time constants are involved. In order to draw-out the true flux variation, a convolution type method is to be used. As a result of the time discretization of the linear differential system that couples the SPND current to the neutron flux, one has to use differential equations. The resolution of these equations is equivalent to an approximately inversion of the initial system. The numerical method described above has been applied in a microcomputer system, in order to treat the SPND signal by a computer-driven millivolmeter. Nowadays, devices for transient experiments in the SILOE reactor are driven by a P.C. system, based on this numerical approach and using an independent data acquisition; the reliability and the ergonomics aspects have been taken into account. The modular conception of the system allows easy further developments for flux monitoring in various surroundings

  16. Tracking the shape-dependent sintering of platinum-rhodium model catalysts under operando conditions.

    Science.gov (United States)

    Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

    2016-01-01

    Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum-rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio. PMID:26957204

  17. Tracking the shape-dependent sintering of platinum–rhodium model catalysts under operando conditions

    Science.gov (United States)

    Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

    2016-01-01

    Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum–rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio. PMID:26957204

  18. Tris-(1,3-diaryltriazenide) complexes of rhodium - Synthesis, structure and, spectral and electrochemical properties

    Indian Academy of Sciences (India)

    Chhandasi Guharoy; Michael G B Drew; Samaresh Bhattacharya

    2009-05-01

    Reaction of 1,3-diaryltriazenes (abbreviated in general as HL-R, where R stands for the para-substituent in the aryl fragment and H stands for the dissociable hydrogen atom, R = OCH3, CH3, H, Cl, NO2) with [Rh(PPh3)2(CO)Cl] in ethanol in the presence of NEt3 produces a series of trisdiaryltriazenide complexes of rhodium of type [Rh(L-R)3], where the triazenes are coordinated to rhodium as monoanionic, bidentate N,N-donors. Structure of the [Rh(L-OCH3)3] complex has been determined by X-ray crystallography. The complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. They also fluoresce in the visible region under ambient condition while excited at around 400 nm. Cyclic voltammetry on these complexes shows a Rh(III)-Rh(IV) oxidation (within 0.84-1.67 V vs SCE), followed by an oxidation of the coordinated triazene ligand (except the R = NO2 complex). An irreversible reduction of the coordinated triazene is also observed for all the complexes below -1.03 V vs SCE.

  19. Rhodium(III)-Catalyzed C-H Activation/Annulation with Vinyl Esters as an Acetylene Equivalent

    OpenAIRE

    Webb, NJ; Marsden, SP; Raw, SA

    2014-01-01

    The behavior of electron-rich alkenes in rhodium-catalyzed C–H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed

  20. Selective Synthesis of Isoquinolines by Rhodium(III)-Catalyzed C-H/N-H Functionalization with α-Substituted Ketones.

    Science.gov (United States)

    Li, Jie; Zhang, Zhao; Tang, Mengyao; Zhang, Xiaolei; Jin, Jian

    2016-08-01

    A rhodium(III)-catalyzed C-H/N-H bond functionalization for the synthesis of 1-aminoisoquinolines from aryl amidines and α-MsO/TsO/Cl ketones was achieved under mild reaction conditions. Thus, this approach provides a practical method for the site-selective synthesis of various synthetically valuable isoquinolines with wide functional group tolerance. PMID:27441726

  1. PipPhos and MorfPhos : Privileged monodentate phosphoramidite ligands for rhodium-catalyzed asymmetric hydrogenation

    NARCIS (Netherlands)

    Bernsmann, Heiko; van den Berg, M; Hoen, Robert; Minnaard, AJ; Mehler, G; Reetz, MT; De Vries, JG; Feringa, BL

    2005-01-01

    A library of 20 monodentate phosphoramidite ligands has been prepared and applied in rhodium-catalyzed asymmetric hydrogenation. This resulted in the identification of two ligands, PipPhos and MorfPhos, that afford excellent and in several cases unprecedented enantioselectivities in the hydrogenatio

  2. Molecular Intercalation and Cohesion of Organic Bulk Heterojunction Photovoltaic Devices

    KAUST Repository

    Bruner, Christopher

    2013-01-17

    The phase separated bulk heterojunction (BHJ) layer in BHJ polymer:fullerene organic photovoltaic devices (OPV) are mechanically weak with low values of cohesion. Improved cohesion is important for OPV device thermomechanical reliability. BHJ devices are investigated and how fullerene intercalation within the active layer affects cohesive properties in the BHJ is shown. The intercalation of fullerenes between the side chains of the polymers poly(3,3″′-didocecyl quaterthiophene) (PQT-12) and poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (pBTTT) is shown to enhance BHJ layer cohesion. Cohesion values range from ≈1 to 5 J m -2, depending on the polymer:fullerene blend, processing conditions, and composition. Devices with non-intercalated BHJ layers are found to have significantly reduced values of cohesion. The resulting device power conversion efficiencies (PCE) are also investigated and correlated with the device cohesion. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

    Science.gov (United States)

    West, William C.; Whitacre, Jay F.; Leifer, Nicole; Greenbaum, Steve; Smart, Marshall; Bugga, Ratnakumar; Blanco, Mario; Narayanan, S. R.

    2007-01-01

    We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and B-11 nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.

  4. Transport study of electrochemically decorated and intercalated graphene

    Science.gov (United States)

    Efetov, Dmitri K.; Mak, Kin Fai; Guo, Yinsheng; Heinz, Tony F.; Brus, Louis; Kim, Philip

    2012-02-01

    Due to the surface-only properties of graphene, the decoration and/or intercalation of single, bi- and multi-layer graphene with foreign atoms can severely modify its electronic interactions, similar to those observed in its 3D counterpart the graphite intercalation compounds. Supported by a highly increased density of state due to a strong charge transfer above 10^14 cm-2 into the graphene π-bands, certain adatoms are expected to induce strong electronic interactions to the graphenes own Dirac fermions, where theoretical predictions reach from the Kondo-effect and magnetism to as far as superconductivity in graphene. In this study we will present evidence of specific adsorption and intercalation of diverse atomic species by electrochemical means. We will present a detailed transport study, including resistivity-, Hall- and magneto-resistivity measurements of single-, bi- and multi-layer graphene devices which were subjected to electrochemical doping by a variety of electrolytes and ionic species such as Li^+, ClO4^-, Cs^+, Ca^2+, etc.

  5. Crystal structures of superconducting sodium intercalates of hafnium nitride chloride

    International Nuclear Information System (INIS)

    Sodium intercalation compounds of HfNCl have been prepared at room temperature in naphtyl sodium solutions in tetrahydrofuran and their crystal structure has been investigated by Rietveld refinement using X-ray powder diffraction data and high-resolution electron microscopy. The structure of two intercalates with space group R3-bar m and lattice parameters a=3.58131(6)A, c=57.752(6)A, and a=3.58791(8)A, c=29.6785(17)A is reported, corresponding to the stages 2 and 1, respectively, of NaxHfNCl. For the stage 2 phase an ordered model is presented, showing two crystallographically independent [HfNCl] units with an alternation of the Hf-Hf interlayer distance along the c-axis, according with the occupation by sodium atoms of one out of two van der Waals gaps. Both stages 1 and 2 phases are superconducting with critical temperatures between 20 and 24K, they coexist in different samples with proportions depending on the synthesis conditions, and show a variation in c spacing that can be correlated with the sodium stoichiometry. High-resolution electron microscopy images of the host and intercalated samples show bending of the HfNCl bilayers as well as stacking faults in some regions, which coexist in the same crystal with ordered domains

  6. Ge-intercalated graphene: The origin of the p-type to n-type transition

    KAUST Repository

    Kaloni, Thaneshwor P.

    2012-09-01

    Recently huge interest has been focussed on Ge-intercalated graphene. In order to address the effect of Ge on the electronic structure, we study Ge-intercalated free-standing C 6 and C 8 bilayer graphene, bulk C 6Ge and C 8Ge, as well as Ge-intercalated graphene on a SiC(0001) substrate, by density functional theory. In the presence of SiC(0001), there are three ways to obtain n-type graphene: i) intercalation between C layers; ii) intercalation at the interface to the substrate in combination with Ge deposition on the surface; and iii) cluster intercalation. All other configurations under study result in p-type states irrespective of the Ge coverage. We explain the origin of the different doping states and establish the conditions under which a transition occurs. © Copyright EPLA, 2012.

  7. Structural Basis for Bulky-Adduct DNA-Lesion Recognition by the Nucleotide Excision Repair Protein Rad14.

    Science.gov (United States)

    Simon, Nina; Ebert, Charlotte; Schneider, Sabine

    2016-07-25

    Heterocyclic aromatic amines react with purine bases and result in bulky DNA adducts that cause mutations. Such structurally diverse lesions are substrates for the nucleotide excision repair (NER). It is thought that the NER machinery recognises and verifies distorted DNA conformations, also involving the xeroderma pigmentosum group A and C proteins (XPA, XPC) that act as a scaffold between the DNA substrate and several other NER proteins. Here we present the synthesis of DNA molecules containing the polycyclic, aromatic amine C8-guanine lesions acetylaminophenyl, acetylaminonaphthyl, acetylaminoanthryl, and acetylaminopyrenyl, as well as their crystal structures in complex with the yeast XPA homologue Rad14. This work further substantiates the indirect lesion-detection mechanism employed by the NER system that recognises destabilised and deformable DNA structures. PMID:27223336

  8. [Magnetic resonance tomography in the diagnosis of nonorganic bulky masses of the retroperitoneal space. Part 1. Cysts, abscesses and flegmons].

    Science.gov (United States)

    Dombrovskiĭ, V I

    2003-01-01

    The paper considers the diagnostic capacities of magnetic resonance imaging (MRI) in detecting non-organic bulky masses of the retroperitoneal space. Based on the analysis of tomographic findings in 23 patients with non-organic cysts of the retroperitoneal space and 27 patients with its abscesses and phlegmons, the first part of the paper describes the MRI semiotics of these diseases in detail and proposes methodic approaches to their identification. Comparison of the data of MRI and pathomorphological analysis of operation materials has yielded the rates of sensitivity, specificity, and accuracy of the method, which are equal to 100, 88.5, and 94.2% for non-organic cysts and 100, 87.1, and 93.5%, respectively. The authors note the lower efficiency of MRI in recognizing hydatid cysts and foreign bodies than ultrasound study and X-ray computed tomography and show it necessary to take into account clinical information in making a radiological conclusion.

  9. Increased micronuclei and bulky DNA adducts in cord blood after maternal exposures to traffic-related air pollution

    DEFF Research Database (Denmark)

    Pedersen, M.; Wichmann, J.; Autrup, H.;

    2009-01-01

    Exposure to traffic-related air pollution in urban environment is common and has been associated with adverse human health effects. In utero exposures that result in DNA damage may affect health later in life. Early effects of maternal and in utero exposures to traffic-related air pollution were...... highest among mother-newborn pairs who lived near medium-traffic-density (> 400-2500 vehicle km/24 h; p 2500 vehicle km/24 h) were significantly increased (p = 0.02). This trend remained after adjusting...... for potential confounders and effect modifiers. For the first time increased bulky DNA adducts and MN in cord blood after maternal exposures to traffic-related air pollution are found, demonstrating that these transplacental environmental exposures induce DNA damage in newborns. Given that increased DNA damage...

  10. Synthesis and characterization of novel polyamide-ethers based on bis-imidazole containing bulky aryl pendant groups

    Directory of Open Access Journals (Sweden)

    Seyed Mahdi Saadati

    2013-01-01

    Full Text Available A series of novel polyamide-ethers (PAEs based on bis-imidazole containing bulky aryl pendant groups was prepared by direct polycondensation of a diamine, 4-(1-(4-(4-(2-(4-aminophenyl-4,5-diphenyl-1H-imidazol-1-ylphenoxyphenyl-4,5-diphenyl-1H-imidazol-2-ylbenzenamine (DABI, and various dicarboxylic acids. All the resulting polyamide-ethers were amorphous with inherent viscosities ranged from 0.52 to 0.61 dL/g and were readily soluble in many organic solvents which could be solution-cast into transparent and tough films. The glass transition temperatures (Tg of these polymers were affected considerably by their chemical structure and ranged from 230 to 310 ºC. They had useful levels of thermal stability associated with relatively high temperatures of 10% weight loss (T10 in the range of 329-399 ºC in air atmosphere.

  11. Synthesis of ACECLOFENAC/HYDROXYPROPYL-β-CYCLODEXTRIN Intercalated Layered Double Hydroxides and Controlled Release Properties

    Science.gov (United States)

    Li, Shifeng; Shen, Yanming; Liu, Dongbin; Fan, Lihui; Wu, Keke; Xiao, Min

    2013-06-01

    Aceclofenac (AC)/hydroxypropyl-β-cyclodextrin (HP-β-CD) complex intercalated layered double hydroxides (LDHs) have been synthesized by reconstruction method. X-ray diffraction, Fourier transform infrared and thermal gravimetric analyses indicated a successful intercalation of AC/HP-β-CD complex into the LDHs gallery. The AC release properties were also studied in different pH values buffer solution. The results indicate that the AC/HP-β-CD intercalated LDH has a potential application in drug delivery agent.

  12. Bi_2WO_6 quantum dot-intercalated ultrathin montmorillonite nanostructure and its enhanced photocatalytic performance

    OpenAIRE

    Sun, Songmei; WANG, WENZHONG; Jiang, Dong; Zhang, Ling; Li, Xiaoman; Yali, Zheng; An, Qi

    2014-01-01

    The kinetic competition between electron-hole recombination and water oxidation is a key limitation for the development of efficient solar water splitting materials. In this study, we present a solution for solving this challenge by constructing a quantum dot-intercalated nanostructure. For the first time, we show the interlayer charge of the intercalated nanostructure can significantly inhibit the electron-hole recombination in photocatalysis. For Bi_2WO_6 quantum dots (QDs) intercalated in ...

  13. Linkage structures strongly influence the binding cooperativity of DNA intercalators conjugated to triplex forming oligonucleotides.

    OpenAIRE

    1994-01-01

    Conjugation of DNA intercalators to triple helix forming oligodeoxynucleotides (ODN's) can enhance ODN binding properties and consequently their potential ability to modulate gene expression. To test the hypothesis that linkage structure could strongly influence the binding enhancement of intercalator conjugation with triplex forming ODN's, we have used a model system to investigate binding avidity of short oligomers conjugated to DNA intercalators through various linkages. Using a dA10.T10 t...

  14. Interlayer Structure of Bioactive Molecule, 2-Aminoethanesulfonate, Intercalated into Calcium-Containing Layered Double Hydroxides

    OpenAIRE

    Tae-Hyun Kim; Hyoung Jun Kim; Jae-Min Oh

    2012-01-01

    We have successfully intercalated 2-aminoethanesulfonate, a well-known biomolecule taurine, into calcium-containing layered double hydroxides via optimized solid phase intercalation. According to X-ray diffraction patterns and infrared spectroscopy, it was revealed that the intercalated taurine molecules were each directly coordinated to other calcium cation and arranged in a zig-zag pattern. Scanning electron microscopy showed that the particle size and morphology of the LDHs were not affect...

  15. Preparation of Fe-intercalated Graphite Based on Coal Tailings, Dimensional Structure

    OpenAIRE

    Irfan Gustian; Eka Angasa; Dwi Agustini; Evi Maryanti; Dyiah Fitriani

    2015-01-01

    Intercalated graphite from coal tailings have been modified through the intercalation of iron. Coal tailings which is a byproduct of the destruction process and flakes washing results from mining coal. Intercalation of iron goal is to improve the physical properties of graphite and modifying sizes of crystal lattice structure with thermal method. Modification process begins with the carbonization of coal tailings at 500ºC and activated with phosphoric acid. Activation process has done by pyro...

  16. 1H MAS NMR characterization of hydrogen over silica-supported rhodium catalyst

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Hydrogen species in both SiO2 and Rh/SiO2 catalysts pretreated indifferent atmospheres (H2, O2, helium or air) at different temperatures (773 or 973 K) were investigated by means of 1H MAS NMR. In SiO2 and O2-pretreated catalysts, a series of downfield signals at ~7.0, 3.8-4.0, 2.0 and 1.5-1.0 were detected. The first two signals can be attributed to strongly adsorbed and physisorbed water and the others to terminal silanol (SiOH) and SiOH under the screening of oxygen vacancies in SiO2 lattice, respectively. Besides the above signals, both upfield signal at ~-110 and downfield signals at 3.0 and 0.0 were also detected in H2-pretreated catalyst, respectively. The upfield signal at ~-110 originated from the dissociative adsorption of H2 over rhodium and was found to consist of both the contributions of reversible and irreversible hydrogen. There also probably existed another dissociatively adsorbed hydrogen over rhodium, which was known to be b hydrogen and in a unique form of "delocalized hydrogen". It was presumed that the b hydrogen had an upfield shift of ca. -20- -50, though its 1H NMR signals, which, having been masked by the spinning sidebands of Si-OH, failed to be directly detected out. The downfield signal at 3.0 was assigned to spillover hydrogen weakly bound by the bridge oxygen of SiO2. Another downfield signal at 0.0 was assigned to hydrogen held in the oxygen vacancies of SiO2 (Si-H species), suffering from the screening of trapped electrons. Both the spillover hydrogen and the Si-H resulted from the migration of the reversible hydrogen and the b hydrogen from rhodium to SiO2 in the close vicinity. It was proved that the above migration of hydrogen was preferred to occur at higher temperature than at lower temperature.

  17. Synthesis, Al3+/Mg2+ Intercalation and Structure Study of Graphite-like Carbon Nitride

    Institute of Scientific and Technical Information of China (English)

    Xifeng Lu; Hongjun Wang; Yi Yang; Tao Liu

    2011-01-01

    Graphite-like carbon nitride (g-C3N4) was synthesized in large quantities at 300℃ under nitrogen by a solidstate reaction route. Furthermore, Al3+ and Mg2+ intercalation of g-C3N4 was performed by an electrochemical method. The starting C3N4 materials and intercalation compounds were characterized by X-ray powder diffraction, Fourier transform infrared spectra, thermogravimetry, transmission electron microscopy, and X-ray photoelectron spectroscopy. The possible structure model of intercalation compounds was proposed. The cation-π interactions and electrostatic interactions were used to explain the changes of microstructure and chemical bonds before and after intercalation.

  18. Mechanism of Si intercalation in defective graphene on SiC

    KAUST Repository

    Kaloni, Thaneshwor P.

    2012-10-01

    Previously reported experimental findings on Si-intercalated graphene on SiC(0001) seem to indicate the possibility of an intercalation process based on the migration of the intercalant through atomic defects in the graphene sheet. We employ density functional theory to show that such a process is in fact feasible and obtain insight into its details. By means of total energy and nudged elastic band calculations we are able to establish the mechanism on an atomic level and to determine the driving forces involved in the different steps of the intercalation process through atomic defects.

  19. Tuning the Properties of Polymer Bulk Heterojunction Solar Cells by Adjusting Fullerene Size to Control Intercalation

    KAUST Repository

    Cates, Nichole C.

    2009-12-09

    We demonstrate that intercalation of fullerene derivatives between the side chains of conjugated polymers can be controlled by adjusting the fullerene size and compare the properties of intercalated and nonintercalated poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (pBTTT):fullerene blends. The intercalated blends, which exhibit optimal solar-cell performance at 1:4 polymer:fullerene by weight, have better photoluminescence quenching and lower absorption than the nonintercalated blends, which optimize at 1:1. Understanding how intercalation affects performance will enable more effective design of polymer:fullerene solar cells. © 2009 American Chemical Society.

  20. The intercalated nuclear complex of the primate amygdala.

    Science.gov (United States)

    Zikopoulos, Basilis; John, Yohan J; García-Cabezas, Miguel Ángel; Bunce, Jamie G; Barbas, Helen

    2016-08-25

    The organization of the inhibitory intercalated cell masses (IM) of the primate amygdala is largely unknown despite their key role in emotional processes. We studied the structural, topographic, neurochemical and intrinsic connectional features of IM neurons in the rhesus monkey brain. We found that the intercalated neurons are not confined to discrete cell clusters, but form a neuronal net that is interposed between the basal nuclei and extends to the dorsally located anterior, central, and medial nuclei of the amygdala. Unlike the IM in rodents, which are prominent in the anterior half of the amygdala, the primate inhibitory net stretched throughout the antero-posterior axis of the amygdala, and was most prominent in the central and posterior extent of the amygdala. There were two morphologic types of intercalated neurons: spiny and aspiny. Spiny neurons were the most abundant; their somata were small or medium size, round or elongated, and their dendritic trees were round or bipolar, depending on location. The aspiny neurons were on average slightly larger and had varicose dendrites with no spines. There were three non-overlapping neurochemical populations of IM neurons, in descending order of abundance: (1) Spiny neurons that were positive for the striatal associated dopamine- and cAMP-regulated phosphoprotein (DARPP-32+); (2) Aspiny neurons that expressed the calcium-binding protein calbindin (CB+); and (3) Aspiny neurons that expressed nitric oxide synthase (NOS+). The unique combinations of structural and neurochemical features of the three classes of IM neurons suggest different physiological properties and function. The three types of IM neurons were intermingled and likely interconnected in distinct ways, and were innervated by intrinsic neurons within the amygdala, or by external sources, in pathways that underlie fear conditioning and anxiety. PMID:27256508

  1. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Science.gov (United States)

    2010-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings...

  2. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis – 2012 Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Thompson, Becky L.

    2012-11-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Testing continued in FY 2012 to further improve the Ir-promoted RhMn catalysts on both silica and carbon supports for producing mixed oxygenates from synthesis gas. This testing re-examined selected alternative silica and carbon supports to follow up on some uncertainties in the results with previous test results. Additional tests were conducted to further optimize the total and relative concentrations of Rh, Mn, and Ir, and to examine selected promoters and promoter combinations based on earlier results. To establish optimum operating conditions, the effects of the process pressure and the feed gas composition also were evaluated.

  3. Screen-printed carbon electrodes modified by rhodium dioxide and glucose dehydrogenase.

    Science.gov (United States)

    Polan, Vojtěch; Soukup, Jan; Vytřas, Karel

    2011-01-01

    The described glucose biosensor is based on a screen-printed carbon electrode (SPCE) modified by rhodium dioxide, which functions as a mediator. The electrode is further modified by the enzyme glucose dehydrogenase, which is immobilized on the electrode's surface through electropolymerization with m-phenylenediamine. The enzyme biosensor was optimized and tested in model glucose samples. The biosensor showed a linear range of 500-5000 mg L(-1) of glucose with a detection limit of 210 mg L(-1) (established as 3σ) and response time of 39 s. When compared with similar glucose biosensors based on glucose oxidase, the main advantage is that neither ascorbic and uric acids nor paracetamol interfere measurements with this biosensor at selected potentials. PMID:21528113

  4. Synthesis, characterization and antibacterial study of cyclometalated rhodium(III) complex containing dithiocarbamate

    Science.gov (United States)

    Mansouri, Ghobad; Heidarizadi, Fateme; Naghipour, Ali; Notash, Behrouz

    2016-10-01

    The novel cyclometalated Rh(III) complex, [Rh(phpy)2(SˆS)], Where phpy is 2-phenylpyridine and (SˆS) is diethyldithiocarbamate, has been prepared and characterized by elemental analysis, IR, 13C and 1H NMR, electronic absorption and Fluorescence spectroscopies, cyclic voltammetry, and X-ray crystallography. The crystal structure of [Rh(phpy)2(SˆS)] shows that the coordination geometry around the Rh(III) is a distorted octahedron, with bite angles of 71.19-81.04° for all three bidentate ligands. Electrochemical analysis by cyclic voltammetry reveals irreversible redox behavior of the rhodium centre. Antibacterial activity of the complex has also been studied by agar disc diffusion method against three Gram-negative bacteria (Pseudomonas aeroginosa, Salmonella typhi and Escherichia coli) and two Gram-positive bacteria (Staphylococcus aureus and Corynebacterium renale).

  5. Determination of palladium, platinum and rhodium in geologic materials by fire assay and emission spectrography

    Science.gov (United States)

    Hapfty, J.; Riley, L.B.

    1968-01-01

    A method is described for the determination of palladium down to 4ppb (parts per billion, 109), platinum down to 10 ppb and rhodium down to 5 ppb in 15 g of sample. Fire-assay techniques are used to preconcentrate the platinum metals into a gold bead, then the bead is dissolved in aqua regia and diluted to volume with 1M hydrochloric acid. The solution is analysed by optical emission spectrography of the residue from 200 ??l of it evaporated on a pair of flat-top graphite electrodes. This method requires much less sample handling than most published methods for these elements. Data are presented for G-1, W-1, and six new standard rocks of the U.S. Geological Survey. The values for palladium in W-1 are in reasonable agreement with previously published data. ?? 1968.

  6. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2011 Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Rummel, Becky L.

    2011-10-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Research during FY 2011 continued to examine the performance of RhMn catalysts on alternative supports including selected zeolite, silica, and carbon supports. Catalyst optimization continued using both the Davisil 645 and Merck Grade 7734 silica supports. Research also was initiated in FY 2011, using the both Davisil 645 silica and Hyperion CS-02C-063 carbon supports, to evaluate the potential for further improving catalyst performance, through the addition of one or two additional metals as promoters to the catalysts containing Rh, Mn, and Ir.

  7. Mapping of the radiation field of a mammography equipment using molybdenum and rhodium filters

    Energy Technology Data Exchange (ETDEWEB)

    Barreira, Jacqueline S.; Campos, Daniela; Vivolo, Vitor, E-mail: jacsales@usp.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2014-07-01

    The use of X rays for diagnostic radiology is very common and important to Medicine, including mammographic diagnosis focusing decreasing of the doses applied to the patients and preserving high quality of the diagnostic image. A quality control program of the irradiation systems it is very necessary. The Instruments Calibration Laboratory (LCI) of IPEN perform calibration in dosemeters used in radiation dosimetry (in diagnostic radiology) for many years. The objective of that paper is determining the point of greatest intensity of the beam issued by the mammography equipment. Exposures were made with filters Rhodium and Molybdenum. That mapping is important before applied a routine quality control program of the mammography equipment and the calibration of instruments in the diagnosis. (author)

  8. Scanning tunneling microscopy studies of organic monolayers adsorbed on the rhodium(111) crystal surface

    Energy Technology Data Exchange (ETDEWEB)

    Cernota, Paul D.

    1999-08-01

    Scanning Tunneling Microscopy studies were carried out on ordered overlayers on the (111) surface of rhodium. These adsorbates include carbon monoxide (CO), cyclohexane, cyclohexene, 1,4-cyclohexadiene, para-xylene, and meta-xylene. Coadsorbate systems included: CO with ethylidyne, CO with para- and meta-xylene, and para-xylene with meta-xylene. In the case of CO, the structure of the low coverage (2x2) overlayer has been observed. The symmetry of the unit cell in this layer suggests that the CO is adsorbed in the 3-fold hollow sites. There were also two higher coverage surface structures with ({radical}7x{radical}7) unit cells. One of these is composed of trimers of CO and has three CO molecules in each unit cell. The other structure has an additional CO molecule, making a total of four. This extra CO sits on a top site.

  9. Hydrogenation of aniline on a low-percentage, supported rhodium catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Ualikhanova, A.; Temirbulatova, A.E.

    1992-01-10

    The products of hydrogenation of aniline and their derivatives exhibit biological activity and are used in the pharmaceutical industry for preparation of analgesic, antipyretic, and sulfanilamide drugs. Up to 30% of the total consumption of aniline is for synthesis of drugs. Hydrogenation of aniline on platinum metals supported on carbon was studied by Rylander et al. The authors investigated the catalytic properties of rhodium supported on oxides in saturation of aniline with hydrogen in water. In most cases, the amount of noble metal in the supported catalyst was 5%. Decreasing the concentration of active phase in the catalyst is economically advantageous. The features of hydrogenation of aniline in the presence of 1% Rh/MgO in solutions with wide variation of the technological parameters of the process were investigated in the present study. 19 refs., 3 figs., 2 tabs.

  10. Ionic Liquids as Solvents for Rhodium and Platinum Catalysts Used in Hydrosilylation Reaction

    Directory of Open Access Journals (Sweden)

    Witold Zielinski

    2016-08-01

    Full Text Available A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product.

  11. Screen-Printed Carbon Electrodes Modified by Rhodium Dioxide and Glucose Dehydrogenase

    Directory of Open Access Journals (Sweden)

    Vojtěch Polan

    2010-01-01

    Full Text Available The described glucose biosensor is based on a screen-printed carbon electrode (SPCE modified by rhodium dioxide, which functions as a mediator. The electrode is further modified by the enzyme glucose dehydrogenase, which is immobilized on the electrode's surface through electropolymerization with m-phenylenediamine. The enzyme biosensor was optimized and tested in model glucose samples. The biosensor showed a linear range of 500–5000 mg L−1 of glucose with a detection limit of 210 mg L−1 (established as 3σ and response time of 39 s. When compared with similar glucose biosensors based on glucose oxidase, the main advantage is that neither ascorbic and uric acids nor paracetamol interfere measurements with this biosensor at selected potentials.

  12. Polaron transitions in charge intercalated amorphous tungsten oxide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Saenger, M.F.; Hofmann, T.; Schubert, M. [Department of Electrical Engineering, and Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln (United States); Hoeing, T. [Flabeg GmbH and Co. KG, Furth im Wald (Germany)

    2008-04-15

    We present a parametric dielectric function model in dependence of the intercalated charge per tungsten ion ratio x, which excellently describes the ellipsometric experimental data, and allows the identification of two polaron modes corresponding to transitions between W{sup 4+} and W{sup 5+} and between W{sup 5+} and W{sup 6+} tungsten ion sites. A competitive relation between the two polaron transitions is found. An empirical relation for the amplitude of the polaron transitions is found useful to provide a good description of the polaron transition dependence on x. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  13. Antiferro quadrupolar ordering in Fe intercalated few layers graphene

    Directory of Open Access Journals (Sweden)

    Abu Jahid Akhtar

    2013-07-01

    Full Text Available The π electron cloud above and below the honeycomb structure of graphene causes each carbon atom to carry a permanent electric quadrupole moment which can attach any cation to impart interesting physical properties. We have synthesized Fe intercalated graphene structures to investigate tunable magnetic properties as a result of this chemical modification. An interesting antiferro quadrupolar ordering is observed which arises due to a coupling between magnetic dipole moment of Fe and electric quadrupole moment on graphene surface. In contrast to antiferromagnetic Neel temperature (TN, here the ordering temperature (TQ increases from 35.5 K to 47.5 K as the magnetic field is raised upto 1 Tesla.

  14. DNA intercalator stimulates influenza transcription and virus replication

    Directory of Open Access Journals (Sweden)

    Poon Leo LM

    2011-03-01

    Full Text Available Abstract Influenza A virus uses its host transcription machinery to facilitate viral RNA synthesis, an event that is associated with cellular RNA polymerase II (RNAPII. In this study, various RNAPII transcription inhibitors were used to investigate the effect of RNAPII phosphorylation status on viral RNA transcription. A low concentration of DNA intercalators, such as actinomycin D (ActD, was found to stimulate viral polymerase activity and virus replication. This effect was not observed in cells treated with RNAPII kinase inhibitors. In addition, the loss of RNAPIIa in infected cells was due to the shift of nonphosphorylated RNAPII (RNAPIIa to hyperphosphorylated RNAPII (RNAPIIo.

  15. C-13 nuclear magnetic resonance in graphite intercalation compounds

    Science.gov (United States)

    Tsang, T.; Resing, H. A.

    1985-01-01

    The C-13 NMR chemical shifts of graphite intercalation compounds have been calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about - 140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal-conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

  16. Capacitors on the basis of intercalate GaSe

    Directory of Open Access Journals (Sweden)

    Kovalyuk Z. D.

    2010-06-01

    Full Text Available The compound GaSe is obtained by the technique of intercalation of a GaSe single crystal in a melt of the ferroelectric salt KNO3. The x-ray analysis of its crystal structure has been carried out and dielectric frequency characteristics of samples has been measured. It is estab-lished, that accumulation of electric charges occurs in the examined examples in frequency area 100—1000 Hz. A sample of filter capacitor has been created on the basis of the re-ceived compounds.

  17. Preparation and capacitive properties of lithium manganese oxide intercalation compound

    International Nuclear Information System (INIS)

    Lithium manganese oxide intercalation compound (Li0.7MnO2) supported on titanium nitride nanotube array (TiN NTA) was applied as cathode electrode material for lithium-ion supercapacitor application. Li0.7MnO2/TiN NTA was fabricated through electrochemical deposition and simultaneous intercalation process using TiN NTA as a substrate, Mn(CH3COO)2 as manganese source, and Li2SO4 as lithium source. The morphology and microstructure of the Li0.7MnO2/TiN NTA were characterized by scanning electron microscopy and X-ray diffraction analysis. The electrochemical performance of the Li0.7MnO2/TiN NTA was investigated by electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge measurements. Li0.7MnO2/TiN NTA exhibited higher capacitive performance in Li2SO4 electrolyte solution rather than that in Na2SO4 electrolyte solution, which was due to the different intercalation effects of lithium-ion and sodium-ion. The specific capacitance was improved from 503.3 F g−1 for MnO2/TiN NTA to 595.0 F g−1 for Li0.7MnO2/TiN NTA at a current density of 2 A g−1 in 1.0 M Li2SO4 electrolyte solution, which was due to the intercalation of lithium-ion for Li0.7MnO2. Li0.7MnO2/TiN NTA also kept 90.4 % capacity retention after 1000 cycles, presenting a good cycling stability. An all-solid-state lithium-ion supercapacitor was fabricated and showed an energy density of 82.5 Wh kg−1 and a power density of 10.0 kW kg−1

  18. Intercalation of small hydrophobic molecules in lipid bilayers containing cholesterol

    Energy Technology Data Exchange (ETDEWEB)

    Worcester, D.L.; Hamacher, K.; Kaiser, H.; Kulasekere, R.; Torbet, J. [Univ. of Missouri, Columbia, MO (United States)

    1994-12-31

    Partitioning of small hydrophobic molecules into lipid bilayers containing cholesterol has been studied using the 2XC diffractometer at the University of Missouri Research Reactor. Locations of the compounds were determined by Fourier difference methods with data from both deuterated and undeuterated compounds introduced into the bilayers from the vapor phase. Data fitting procedures were developed for determining how well the compounds were localized. The compounds were found to be localized in a narrow region at the center of the hydrophobic layer, between the two halves of the bilayer. The structures are therefore intercalated structures with the long axis of the molecules in the plane of the bilayer.

  19. Preparation and capacitive properties of lithium manganese oxide intercalation compound

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Fang; Xie, Yibing, E-mail: ybxie@seu.edu.cn [Southeast University, School of Chemistry and Chemical Engineering (China)

    2015-12-15

    Lithium manganese oxide intercalation compound (Li{sub 0.7}MnO{sub 2}) supported on titanium nitride nanotube array (TiN NTA) was applied as cathode electrode material for lithium-ion supercapacitor application. Li{sub 0.7}MnO{sub 2}/TiN NTA was fabricated through electrochemical deposition and simultaneous intercalation process using TiN NTA as a substrate, Mn(CH{sub 3}COO){sub 2} as manganese source, and Li{sub 2}SO{sub 4} as lithium source. The morphology and microstructure of the Li{sub 0.7}MnO{sub 2}/TiN NTA were characterized by scanning electron microscopy and X-ray diffraction analysis. The electrochemical performance of the Li{sub 0.7}MnO{sub 2}/TiN NTA was investigated by electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge measurements. Li{sub 0.7}MnO{sub 2}/TiN NTA exhibited higher capacitive performance in Li{sub 2}SO{sub 4} electrolyte solution rather than that in Na{sub 2}SO{sub 4} electrolyte solution, which was due to the different intercalation effects of lithium-ion and sodium-ion. The specific capacitance was improved from 503.3 F g{sup −1} for MnO{sub 2}/TiN NTA to 595.0 F g{sup −1} for Li{sub 0.7}MnO{sub 2}/TiN NTA at a current density of 2 A g{sup −1} in 1.0 M Li{sub 2}SO{sub 4} electrolyte solution, which was due to the intercalation of lithium-ion for Li{sub 0.7}MnO{sub 2}. Li{sub 0.7}MnO{sub 2}/TiN NTA also kept 90.4 % capacity retention after 1000 cycles, presenting a good cycling stability. An all-solid-state lithium-ion supercapacitor was fabricated and showed an energy density of 82.5 Wh kg{sup −1} and a power density of 10.0 kW kg{sup −1}.

  20. Effect of a bulky lateral substitution by chlorine atom and methoxy group on self-assembling properties of lactic acid derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Stojanović, Maja, E-mail: maja.stojanovic@df.uns.ac.rs [Department of Physics, Faculty of Sciences, University of Novi Sad, Trg D.Obradovića 4, 21000 Novi Sad (Serbia); Bubnov, Alexej [Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Prague (Czech Republic); Obadović, Dušanka Ž. [Department of Physics, Faculty of Sciences, University of Novi Sad, Trg D.Obradovića 4, 21000 Novi Sad (Serbia); Hamplová, Věra [Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Prague (Czech Republic); Cvetinov, Miroslav [Department of Physics, Faculty of Sciences, University of Novi Sad, Trg D.Obradovića 4, 21000 Novi Sad (Serbia); Kašpar, Miroslav [Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Prague (Czech Republic)

    2014-07-01

    Several chiral liquid crystalline materials derived from the lactic acid have been studied with the aim to establish the effect of bulky lateral substituents on their self-assembling properties. A chlorine atom and methoxy group have been used as lateral substituents in ortho position to ether group position on phenyl ring far from the chiral centre. All the studied materials possess tilted ferroelectric smectic C* phase in a broad temperature range. In dependence on the molecular structure namely type of lateral substituent and length of the chiral chain, the cholesteric mesophase, orthogonal paraelectric smectic A* and crystal mesophases have been detected. Lateral chlorine substitution results in decrease of both the clearing point and crystallisation temperature as well as in a distinct increase of spontaneous polarization. Bulky methoxy substitution slightly suppresses the spontaneous polarisation but strongly increases the melting point that results in monotropic peculiarity of the SmC* phase. Mesomorphic, spontaneous, structural and dielectric properties of the substituted compounds were established and compared to those of the non-substituted ones in order to contribute to better understanding of the structure–property relationship for such chiral self-assembling materials. - Highlights: • Chiral liquid crystalline materials derived from the lactic acid have been studied. • Effect of bulky lateral substituents on self-assembling properties has been established. • Bulky methoxy substitution suppresses spontaneous polarisation but increases the melting point. • The compounds might have a strong potential for many advanced electro-optic applications.

  1. Duplex-Selective Ruthenium-based DNA Intercalators

    Science.gov (United States)

    Shade, Chad M.; Kennedy, Robert D.; Rouge, Jessica L.; Rosen, Mari S.; Wang, Mary X.; Seo, Soyoung E.; Clingerman, Daniel J.

    2016-01-01

    We report the design and synthesis of small molecules that exhibit enhanced luminescence in the presence of duplex rather than single-stranded DNA. The local environment presented by a well-known [Ru(dipyrido[2,3-a:3',2'-c]phenazine)L2]2+-based DNA intercalator was modified by functionalizing the bipyridine ligands with esters and carboxylic acids. By systematically varying the number and charge of the pendant groups, it was determined that decreasing the electrostatic interaction between the intercalator and the anionic DNA backbone reduced single-strand interactions and translated to better duplex specificity. In studying this class of complexes, a single RuII complex emerged that selectively luminesces in the presence of duplex DNA with little to no background from interacting with single stranded DNA. This complex shows promise as a new dye capable of selectively staining double versus single-stranded DNA in gel electrophoresis, which cannot be done with conventional SYBR dyes. PMID:26119581

  2. Microscopic physical and chemical properties of graphite intercalation compounds

    Energy Technology Data Exchange (ETDEWEB)

    Eklund, P.C.

    1992-08-24

    Optical spectroscopy (Raman, FTIR and Reflection ) was used to study a variety of acceptor- and donor-type compounds synthesized to determine the microscopic models consistent with the spectrocsopic results. General finding is that the electrical conduction properties of these compounds can be understood on the basis that the intercalation of atomic and/or molecular species between the host graphite layers either raises or lowers the Fermi level (E{sub F)} in a graphitic band structure. This movement of E{sub F} is accomplished via a charge transfer of electrons from the intercalate layers to the graphitic layers (donor compounds), or vice versa (acceptor compounds). Furthermore, the band structure must be modified to take into account the layers of charge that occur as a result of the charge transfer. This charge layering introduces additional bands of states near E{sub F}, which are discussed. Charge-transfer also induces a perturbation of the graphitic normal mode frequencies which can be understood as the result of a contraction (acceptor compounds) or expansion (donor compounds) of the intralayer C-C bonds. Ab-initio calculations support this view and are in reasonable agreement with experimental data.

  3. Superconductivity of graphite intercalation compounds with alkali-metal amalgams

    International Nuclear Information System (INIS)

    Superconductivity of the alkali-metal amalgam graphite intercalation compounds of stage 1 (C4KHg, C4RbHg) and stage 2 (C8KHg, C8RbHg) has been studied as well as that of the pristine amalgams (KHg, RbHg). The transition temperatures are 0.73, 0.99, 1.90, and 1.40 K for C4KHg, C4RbHg, C8KHg, and C8RbHg, respectively. The critical-field anisotropy ratio H/sup parallel//sub c/2/H/sup perpendicular//sub c/2 is about 10 for the stage 1 and about 15 to 40 for the stage 2. It is argued that electrons in the intercalant bands rather than the graphitic bands play the main role in the superconductivity. An interesting feature is that the stage-2 compound, which has a lower density of states at the Fermi level, has a higher transition temperature than the corresponding state-1 compound

  4. Methotrexate intercalated ZnAl-layered double hydroxide

    Science.gov (United States)

    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.

  5. Scaling Relations for Intercalation Induced Damage in Electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Chien-Fan; Barai, Pallab; Smith, Kandler; Mukherjee, Partha P.

    2016-06-01

    Mechanical degradation, owing to intercalation induced stress and microcrack formation, is a key contributor to the electrode performance decay in lithium-ion batteries (LIBs). The stress generation and formation of microcracks are caused by the solid state diffusion of lithium in the active particles. In this work, scaling relations are constructed for diffusion induced damage in intercalation electrodes based on an extensive set of numerical experiments with a particle-level description of microcrack formation under disparate operating and cycling conditions, such as temperature, particle size, C-rate, and drive cycle. The microcrack formation and evolution in active particles is simulated based on a stochastic methodology. A reduced order scaling law is constructed based on an extensive set of data from the numerical experiments. The scaling relations include combinatorial constructs of concentration gradient, cumulative strain energy, and microcrack formation. The reduced order relations are further employed to study the influence of mechanical degradation on cell performance and validated against the high order model for the case of damage evolution during variable current vehicle drive cycle profiles.

  6. Preparation of PAA/AM/MMT Hybrid by Intercalation Polymerization

    Institute of Scientific and Technical Information of China (English)

    WANG; YunPu

    2001-01-01

    Over the last few years, Montmorillonite (MMT) was widely used as a special inorganic material for preparing Polymer/MMT nanocompsites. MMT is a clay imineral consisting of stacked silicate sheets whose thickness is about 10A. Through intercalation a large number of polymer-clay nanocomposites have been prepared such as Nylon-clay hybrid [1], PS-clay hybrid [2], Poly (methyl methacrylate) (PMMA)-clay hybrid [3], etc.  In this article, the synthesis and properties of Poly (acrylic acid/acrylamide)/MMT hybrid (PAAAM/MMT) were studied. X-ray diffraction and Transmission electron microscopy were used to characterize the hybrid material. DSC has been used to study its property. Results showed that the intercalating reagents have entered the space of MMT's layers and enlarged them. At the same time, the MMT dispersed homogeneously in acrylic acid and acrylamide monomers that allow MMT to disperse in PAAAM matrix in the monolayer form.  ……

  7. ROLE OF THE INTERCALATED DISC IN CARDIAC PROPAGATION AND ARRHYTHMOGENESIS

    Directory of Open Access Journals (Sweden)

    Andre Georges Kleber

    2014-10-01

    Full Text Available AbstractThis review article discusses mechanisms underlying impulse propagation in cardiac muscle with specific emphasis on the role of the cardiac cell-to-cell junction, called the intercalated disc. The first part of this review deals with the role of gap junction channels, formed by connexin proteins, as a determinant of impulse propagation. It is shown that, depending on the underlying structure of the cellular network, decreasing the conductance of gap junction channels (so-called electrical uncoupling may either only slow, or additionally stabilize propagation and reverse unidirectional propagation block to bidirectional propagation. This is because the safety factor for propagation increases with decreasing intercellular electrical conductance. The role of heterogeneous connexin expression, which may be present in disease states, is also discussed. The hypothesis that so-called ephaptic impulse transmission plays a role in heart and can substitute for electrical coupling has been revived recently. Whereas ephaptic transmission can be demonstrated in theoretical simulations, direct experimental evidence has not yet been presented.The second part of this review deals with the interaction of three protein complexes at the intercalated disc: (1 desmosomal and adherers junction proteins, (2 ion channel proteins, and (3 gap junction channels consisting of connexins. Recent work has revealed multiple interactions between these three protein complexes which occur, at least in part, at the level of protein trafficking. Such interactions are likely to play an important role in the pathogenesis of arrhythmogenic cardiomyopathy, and may reveal new therapeutic concepts and targets.

  8. Potassium-intercalated H2Pc films : Alkali-induced electronic and geometrical modifications

    NARCIS (Netherlands)

    Nilson, K.; Ahlund, J.; Shariati, M. -N.; Schiessling, J.; Palmgren, P.; Brena, B.; Gothelid, E.; Hennies, F.; Huismans, Y.; Evangelista, F.; Rudolf, P.; Gothelid, M.; Martensson, N.; Puglia, C.; Åhlund, J.; Göthelid, E.; Göthelid, M.; Mårtensson, N.

    2012-01-01

    X-ray spectroscopy studies of potassium intercalated metal-free phthalocyanine multilayers adsorbed on Al(110) have been undertaken. Photoelectron spectroscopy measurements show the presence of several charge states of the molecules upon K intercalation, due to a charge transfer from the alkali. In

  9. Thermal Stability of Modified i-Motif Oligonucleotides with Naphthalimide Intercalating Nucleic Acids

    DEFF Research Database (Denmark)

    El-Sayed, Ahmed Ali; Pedersen, Erik B.; Khaireldin, Nahid Y.

    2016-01-01

    naphthalimide (1H-benzo[de]isoquinoline-1,3(2H)-dione) as the intercalating nucleic acid. The stabilities of i-motif structures with inserted naphthalimide intercalating nucleotides were studied using UV melting temperatures (Tm) and circular dichroism spectra at different pH values and conditions (crowding and...

  10. Impedance Simulation of a Li-Ion Battery with Porous Electrodes and Spherical Li+ Intercalation Particles

    NARCIS (Netherlands)

    Huang, R.W.J.M.; Chung, F.; Kelder, E.M.

    2006-01-01

    We present a semimathematical model for the simulation of the impedance spectra of a rechargeable lithium batteries consisting of porous electrodes with spherical Li+ intercalation particles. The particles are considered to have two distinct homogeneous phases as a result of the intercalation and de

  11. X-ray photoelectron spectroscopy as a probe of the interaction between rhodium acetate and ionic liquids

    Science.gov (United States)

    Men, Shuang; Jiang, Jing

    2016-02-01

    X-ray photoelectron spectroscopy (XPS) is used as a probe of the interaction between rhodium acetate ([Rh2(OAc)4]) and ionic liquids. Due to the impact of the anion of ionic liquids on the electronic environment of the rhodium centre, the measured Rh 3d binding energies of [Rh2(OAc)4] dissolved in a series of ionic liquids were found to decrease along with the increasing of the basicity of anions. The reduction of Rh(II) to Rh(0) in 1-octyl-3methylimidazolium acetate ([C8C1Im][OAc]) under UHV condition was monitored by XPS. The intensity of the new formed metallic Rh(0) peak was found increased along with time. The surface enrichment of the new formed Rh(0) species in the system was also concluded.

  12. Effects of Bulky Substituents of Push-Pull Porphyrins on Photovoltaic Properties of Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Higashino, Tomohiro; Kawamoto, Kyosuke; Sugiura, Kenichi; Fujimori, Yamato; Tsuji, Yukihiro; Kurotobi, Kei; Ito, Seigo; Imahori, Hiroshi

    2016-06-22

    To evaluate the effects of substituent bulkiness around a porphyrin core on the photovoltaic properties of porphyrin-sensitized solar cells, long alkoxy groups were introduced at the meso-phenyl group (ZnPBAT-o-C8) and the anchoring group (ZnPBAT-o-C8Cn, n = 4, 8) of an asymmetrically substituted push-pull porphyrin with double electron-donating diarylamino groups and a single electron-withdrawing carboxyphenylethynyl anchoring group. The spectroscopic and electrochemical properties of ZnPBAT-o-C8 and ZnPBAT-o-C8Cn were found to be superior to those of a push-pull porphyrin reference (YD2-o-C8), demonstrating their excellent light-harvesting and redox properties for dye-sensitized solar cells. A power conversion efficiency (η) of the ZnPBAT-o-C8-sensitized solar cell (η = 9.1%) is higher than that of the YD2-o-C8-sensitized solar cell (η = 8.6%) using iodine-based electrolyte due to the enhanced light-harvesting ability of ZnPBAT-o-C8. In contrast, the solar cells based on ZnPBAT-o-C8Cn, possessing the additional alkoxy chains in the anchoring group, revealed the lower η values of 7.3% (n = 4) and 7.0% (n = 8). Although ZnPBAT-o-C8Cn exhibited higher resistance at the TiO2-dye-electrolyte interface by virtue of the extra alkoxy chains, the reduced amount of the porphyrins on TiO2 by excessive addition of coadsorbent chenodeoxycholic acid (CDCA) for mitigating the aggregation on TiO2 resulted in the low η values. Meanwhile, the ZnPBAT-o-C8-sensitized solar cell showed the lower η value of 8.1% than the YD2-o-C8-sensitized solar cell (η = 9.8%) using cobalt-based electrolyte. The smaller η value of the ZnPBAT-o-C8-sensitized solar cell may be attributed to the insufficient blocking effect of the bulky substituents of ZnPBAT-o-C8 under the cobalt-based electrolyte conditions. Overall, the alkoxy chain length and substitution position around the porphyrin core are important factors to affect the cell performance.

  13. Rhodium Catalysts in the Oxidation of CO by O2 and NO: Shape, Composition, and Hot Electron Generation

    OpenAIRE

    Renzas, James Russell

    2010-01-01

    AbstractRhodium Catalysts in the Oxidation of CO by O2 and NO: Shape, Composition, and Hot Electron GenerationbyJames Russell RenzasDoctor of Philosophy in ChemistryUniversity of California, BerkeleyProfessor Gabor A. Somorjai, ChairProfessor Stephen R. LeoneProfessor Jeffrey Bokor It is well known that the activity, selectivity, and deactivation behavior of heterogeneous catalysts are strongly affected by a wide variety of parameters, including but not limited to nanoparticle size, ...

  14. Dispersive oxidation of rhodium clusters in Na-Y by the combined action of zeolite protons and carbon monoxide

    International Nuclear Information System (INIS)

    This paper uses x-ray photoelectron spectroscopy, fourier transform infrared spectroscopy and temperature programmed mass-spectrometric analysis to study the interaction of Na-Y supported rhodium with hydrogen, carbon monoxide, and zeolite protons. This report attempts to clarify the mechanism of dispersive oxidation of reduced Rh particles in the presence of CO, leading to the formation of Rh+(CO)2 cations

  15. Rhodium-Catalyzed Acyloxy Migration of Propargylic Esters in Cycloadditions, Inspiration from Recent “Gold Rush”

    OpenAIRE

    Shu, Xing-Zhong; Shu, Dongxu; Schienebeck, Casi M.; TANG, WEIPING

    2012-01-01

    Transition metal-catalyzed acyloxy migration of propargylic esters offers versatile entries to allene and vinyl carbene intermediates for various fascinating subsequent transformations. Most π-acidic metals (e.g. gold and platinum) are capable of facilitating these acyloxy migration events. However, very few of these processes involve redox chemistry, which are well-known for most other transition metals such as rhodium. The coupling of acyloxy migration of propargylic esters with oxidative a...

  16. Sequential rhodium/palladium catalysis: enantioselective formation of dihydroquinolinones in the presence of achiral and chiral ligands.

    Science.gov (United States)

    Zhang, Lei; Qureshi, Zafar; Sonaglia, Lorenzo; Lautens, Mark

    2014-12-01

    Compatible combinations of achiral and chiral ligands can be used in rhodium/palladium catalysis to achieve highly enantioselective domino reactions. The difference in rates of catalysis and minimal effects of ligand interference confer control in the domino sequence. The "all-in-one" 1,4-conjugate arylation and C-N cross-coupling through sequential Rh/Pd catalysis provides access to enantioenriched dihydroquinolinone building blocks.

  17. Instability of the rhodium magnetic moment as origin of the metamagnetic phase transition in alpha-FeRh

    OpenAIRE

    Gruner, M. E.; Hoffmann, E.; Entel, P.

    2002-01-01

    Based on ab initio total energy calculations we show that two magnetic states of rhodium atoms together with competing ferromagnetic and antiferromagnetic exchange interactions are responsible for a temperature induced metamagnetic phase transition, which experimentally is observed for stoichiometric alpha-FeRh. A first-principle spin-based model allows to reproduce this first-order metamagnetic transition by means of Monte Carlo simulations. Further inclusion of spacial variation of exchange...

  18. Applying Adjacent Hyperbolas to Calculation of the Upper Limit of the Periodic Table of Elements, with Use of Rhodium

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2011-01-01

    Full Text Available In the earlier study (Khazan A. Upper Limit in Mendeleev’s Periodic Table — Ele- ment No. 155. 2nd ed., Svenska fysikarkivet, Stockholm, 2010 the author showed how Rhodium can be applied to the hyperbolic law of the Periodic Table of Elements in or- der to calculate, with high precision, all other elements conceivable in the Table. Here we obtain the same result, with use of fraction linear functions (adjacent hyperbolas.

  19. Applying Adjacent Hyperbolas to Calculation of the Upper Limit of the Periodic Table of Elements, with Use of Rhodium

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2011-01-01

    Full Text Available In the earlier study (Khazan A. Upper Limit in Mendeleev's Periodic Table - Element No.155. 2nd ed., Svenska fysikarkivet, Stockholm, 2010 the author showed how Rhodium can be applied to the hyperbolic law of the Periodic Table of Elements in order to calculate, with high precision, all other elements conceivable in the Table. Here we obtain the same result, with use of fraction linear functions (adjacent hyperbolas.

  20. Rhodium(i)-catalysed skeletal reorganisation of benzofused spiro[3.3]heptanes via consecutive carbon-carbon bond cleavage.

    Science.gov (United States)

    Matsuda, Takanori; Yuihara, Itaru; Kondo, Kazuki

    2016-08-01

    Skeletal reorganisation of benzofused spiro[3.3]heptanes has been achieved using rhodium(i) catalysts. The reaction of benzofused 2-(2-pyridylmethylene)spiro[3.3]heptanes proceeds via sequential C-C bond oxidative addition and β-carbon elimination. On the other hand, benzofused spiro[3.3]heptan-2-ols undergo two consecutive β-carbon elimination processes. In both cases, substituted naphthalenes are obtained. PMID:27357097

  1. Dynamics of Intercalation/De-Intercalation of Rhodamine B during the Polymorphic Transformation of CdAl Layered Double Hydroxide to the Brucite-Like Cadmium Hydroxide

    KAUST Repository

    Saliba, Daniel

    2016-06-23

    Cadmium-Aluminum layered double hydroxide (CdAl LDH) is thermodynamically unstable and transforms to Cd(OH)2 and Al(OH)3 in a short period of time. We present a reaction-diffusion framework that enables us to use in situ steady-state fluorescence spectroscopy to study the kinetics of intercalation of a fluorescent probe (Rhodamine B (RhB)) during the formation of the CdAl LDH and its de-intercalation upon the conversion of the LDH phase to the β phase (Cd(OH)2). The method involves the diffusion of sodium hydroxide into a hydrogel gel matrix containing the aluminum and cadmium ions as well as the species we wish to incorporate in the interlayers of the LDH. The existence of RhB between the LDH layers and its expel during the transition into the β phase are proved via fluorescence microscopy, XRD and ssNMR. The activation energies of intercalation and de-intercalation of RhB are computed and show dependence on the cationic ratio of the corresponding LDH. We find that the energies of de- intercalation are systematically higher than those of intercalation proving that the dyes are stabilized due to the probe-brucite sheets interactions.

  2. Atomic force microscopy study of anion intercalation into highly oriented pyrolytic graphite

    Energy Technology Data Exchange (ETDEWEB)

    Alliata, D.; Haering, P.; Haas, O.; Koetz, R. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Siegenthaler, H. [University of Berne (Switzerland)

    1999-08-01

    In the context of ion transfer batteries, we studied highly oriented pyrolytic graphite (HOPG) in perchloric acid, as a model to elucidate the mechanism of electrochemical intercalation in graphite. Aim of the work is the local and time dependent investigation of dimensional changes of the host material during electrochemical intercalation processes on the nanometer scale. We used atomic force microscopy (AFM), combined with cyclic voltammetry, as in-situ tool of analysis during intercalation and expulsion of perchloric anions into the HOPG electrodes. According to the AFM measurements, the HOPG interlayer spacing increases by 32% when perchloric anions intercalate, in agreement with the formation of stage IV of graphite intercalation compounds. (author) 3 figs., 3 refs.

  3. Melamine/Stearic Acid Composite Nanowires and Vesicles with an Intercalated Nanostructure Prepared through NCCM Method

    Institute of Scientific and Technical Information of China (English)

    Juan Guo; Dao-yong Chen

    2012-01-01

    A solvent-non-solvent method invented in our laboratory for preparing non-covalently connected micelles (NCCM) was used to intercalate melamine (MA) molecules into stearic acid (SA) bilayers to form the composite nanoparticles with an intercalated nanostructure in which a melamine bilayer is sandwiched between two stearic acid bilayers,NCCM method helps to sufficiently mix the two components in nanospace and meanwhile inhibits the strong tendency of self-crystallization of MA,leading to the intercalation.Although the nanoparticles have a regular inner structure,the primary MA/SA nanoparticles have an irregular morphology.Regular nanoparticles were obtained through annealing the suspension of the primary nanoparticles.Through annealing at different temperatures,the MA/SA composite nanowires and vesicles with an intercalated structure were prepared respectively.It is proposed that the morphological change results from the change in the intercalated structure.

  4. Interlayer Structure of Bioactive Molecule, 2-Aminoethanesulfonate, Intercalated into Calcium-Containing Layered Double Hydroxides

    Directory of Open Access Journals (Sweden)

    Tae-Hyun Kim

    2012-01-01

    Full Text Available We have successfully intercalated 2-aminoethanesulfonate, a well-known biomolecule taurine, into calcium-containing layered double hydroxides via optimized solid phase intercalation. According to X-ray diffraction patterns and infrared spectroscopy, it was revealed that the intercalated taurine molecules were each directly coordinated to other calcium cation and arranged in a zig-zag pattern. Scanning electron microscopy showed that the particle size and morphology of the LDHs were not affected by the solid phase intercalation, and the surface of intercalates was covered by organic moieties. From ninhydrin amine detection tests, we confirmed that most of the taurine molecules were well stabilized between the calcium-containing LDH layers.

  5. Oxygen Intercalation of Graphene on Transition Metal Substrate: An Edge-Limited Mechanism.

    Science.gov (United States)

    Ma, Liang; Zeng, Xiao Cheng; Wang, Jinlan

    2015-10-15

    Oxygen intercalation has been proven to be an efficient experimental approach to decouple chemical vapor deposition grown graphene from metal substrate with mild damage, thereby enabling graphene transfer. However, the mechanism of oxygen intercalation and associated rate-limiting step are still unclear on the molecular level. Here, by using density functional theory, we evaluate the thermodynamics stability of graphene edge on transition metal surface in the context of oxygen and explore various reaction pathways and energy barriers, from which we can identify the key steps as well as the roles of metal passivated graphene edges during the oxygen intercalation. Our calculations suggest that in well-controlled experimental conditions, oxygen atoms can be easily intercalated through either zigzag or armchair graphene edges on metal surface, whereas the unwanted graphene oxidation etching can be suppressed. Oxygen intercalation is, thus, an efficient and low-damage way to decouple graphene from a metal substrate while it allows reusing metal substrate for graphene growth.

  6. Simultaneous nondestructive analysis of palladium, rhodium, platinum, and gold nanoparticles using energy dispersive X-ray fluorescence.

    Science.gov (United States)

    Fiedler, Haidi D; Drinkel, Emma E; Orzechovicz, Beatriz; Leopoldino, Elder C; Souza, Franciane D; Almerindo, Gizelle I; Perdona, Cristian; Nome, Faruk

    2013-11-01

    A selective method is proposed for the determination of palladium, gold, and sulfur in catalytic systems, by direct liquid analysis using energy dispersive X-ray fluorescence (EDXRF), under an atmosphere of helium or air. This method allows a nondestructive analysis of palladium, rhodium, platinum, and gold nanoparticulate catalysts stabilized by imidazolium propane sulfonate based zwitterionic surfactants, allowing the samples to be reused for catalytic studies. The signals from palladium, rhodium, platinum, and gold samples in the presence of imidazolium propane sulfonate-based zwitterionic surfactants obtained using EDXRF before (Pd(2+), Rh(2+), Pt(2+), and Au(3+)) and after (Pd(0), Rh(0), Pt(0), and Au(0)) formation of nanoparticles are essentially identical. The results show that the EDXRF method is nondestructive and allows detection and quantification of the main components of platinum, gold, rhodium, and palladium NPs, including the surfactant concentration, with detection and quantification limits in the range of 0.4-3 mg L(-1). The matrices used in such samples present no problems, even allowing the detection and quantification of interfering elements.

  7. DNA binding and topoisomerase II inhibitory activity of water-soluble ruthenium(II) and rhodium(III) complexes.

    Science.gov (United States)

    Singh, Sanjay Kumar; Joshi, Shweta; Singh, Alok Ranjan; Saxena, Jitendra Kumar; Pandey, Daya Shankar

    2007-12-10

    Water-soluble piano-stool arene ruthenium complexes based on 1-(4-cyanophenyl)imidazole (CPI) and 4-cyanopyridine (CNPy) with the formulas [(eta6-arene)RuCl2(L)] (L = CPI, eta6-arene = benzene (1), p-cymene (2), hexamethylbenzene (3); L = CNPy, eta6-arene = benzene (4), p-cymene (5), hexamethylbenzene (6)) have been prepared by our earlier methods. The molecular structure of [(eta6-C6Me6)RuCl2(CNPy)] (6) has been determined crystallographically. Analogous rhodium(III) complex [(eta5-C5Me5)RhCl2(CPI)] (7) has also been prepared and characterized. DNA interaction with the arene ruthenium complexes and the rhodium complex has been examined by spectroscopic and gel mobility shift assay; condensation of DNA and B-->Z transition have also been described. Arene ruthenium(II) and EPh3 (E = P, As)-containing arene ruthenium(II) complexes exhibited strong binding behavior, however, rhodium(III) complexes were found to be Topo II inhibitors with an inhibition percentage of 70% (7) and 30% (7a). Furthermore, arene ruthenium complexes containing polypyridyl ligands also act as mild Topo II inhibitors (10%, 3c and 40%, 3d) in contrast to their precursor complexes. Complexes 4-6 also show significant inhibition of beta-hematin/hemozoin formation activity. PMID:18001110

  8. Leading research on supermetals. Part 1. Bulky material (iron system); Supermetal no sendo kenkyu. 1. Ogata sozai (tetsukei)

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-03-01

    For further improvement of iron system materials, supermetals with ultimate characteristics were researched. Since their strength and toughness have been improved with grain refinement by thermomechanical treatment, improvement of single-phase steel is nearly completed, and the study on ultra-fine multi-phase steel is indispensable. Bulky materials are also restrained from grain refinement because of the capability of existing processing facilities. Making a breakthrough in such restraint requires a challenge to high-speed rolling, repeated shear deformation and ultra-high strain rate process beyond conventional technologies. Further improvement of microstructure and dynamic characteristics requires other energies such as magnetism as well as mechanical energy. {gamma}-{alpha} phase transition important for structure control of steel materials is dependent on magnetism. The study on structure control and characteristics improvement under ferromagnetic field is essential in the future. Material improvement such as reduction of impurities and circulating elements, environmental measures, and mechanical alloying remain as issues to be studied. 224 refs., 176 figs., 18 tabs.

  9. Total digestibility and in situ degradability of bulky diets with the inclusion of ionophores or probiotics for cattle and buffaloes

    Directory of Open Access Journals (Sweden)

    Lúcia Maria Zeoula

    2014-09-01

    Full Text Available The effects of ionophores (monensin and probiotic (Saccharomyces cerevisiae + selenium + chromium in diets with 80% forage were evaluated on the digestibility of nutrients. Three buffaloes, Murrah (Bubalus bubalis and three cattle, Holstein (Bos taurus, with an average weight of 520 ± 30 kg and 480 ± 182 kg, respectively, with rumen cannula, over experimental design with two 3 x 3 Latin squares in a 3 x 2 factorial arrangement, with the absence or presence of additives: ionophore or probiotic and two species, were used. The internal flow indicator of fecal dry matter (DM was the acid insoluble ash. DM, crude protein (CP and neutral detergent fiber (NDF ruminal degradability of Tifton 85 hay was conducted for cattle and buffaloes. A diet containing probiotics had higher dry matter and organic matter digestibility in buffalo and cattle, indicating a good performance in bulky diets. The potential and effective dry matter degradability in diet with probiotic in buffaloes, were smaller than diet with ionophore, suggesting that there was a better digestion of nutrients in the intestine of these animals. The potential and effective degradability of neutral detergent fiber and crude protein in the diet containing ionophores were superior than diet containing probiotic. Buffaloes showed higher capacity of dry matter and fiber digestion than cattle.

  10. Tuning the self-assembly of the bioactive dipeptide L-carnosine by incorporation of a bulky aromatic substituent.

    Science.gov (United States)

    Castelletto, V; Cheng, G; Greenland, B W; Hamley, I W; Harris, P J F

    2011-03-15

    The dipeptide L-carnosine has a number of important biological properties. Here, we explore the effect of attachment of a bulky hydrophobic aromatic unit, Fmoc [N-(fluorenyl-9-methoxycarbonyl)] on the self-assembly of Fmoc-L-carnosine, i.e., Fmoc-β-alanine-histidine (Fmoc-βAH). It is shown that Fmoc-βAH forms well-defined amyloid fibrils containing β sheets above a critical aggregation concentration, which is determined from pyrene and ThT fluorescence experiments. Twisted fibrils were imaged by cryogenic transmission electron microscopy. The zinc-binding properties of Fmoc-βAH were investigated by FTIR and Raman spectroscopy since the formation of metal ion complexes with the histidine residue in carnosine is well-known, and important to its biological roles. Observed changes in the spectra may reflect differences in the packing of the Fmoc-dipeptides due to electrostatic interactions. Cryo-TEM shows that this leads to changes in the fibril morphology. Hydrogelation is also induced by addition of an appropriate concentration of zinc ions. Our work shows that the Fmoc motif can be employed to drive the self-assembly of carnosine into amyloid fibrils. PMID:21338121

  11. Superconductivity and Intercalation State in the Lithium-Hexamethylenediamine-Intercalated Superconductor Lix(C6H16N2)yFe2-zSe2: Dependence on the Intercalation Temperature and Lithium Content

    Science.gov (United States)

    Hosono, Shohei; Noji, Takashi; Hatakeda, Takehiro; Kawamata, Takayuki; Kato, Masatsune; Koike, Yoji

    2016-10-01

    The superconductivity and intercalation state in the lithium- and hexamethylenediamine (HMDA)-intercalated superconductor Lix(C6H16N2)yFe2-zSe2 have been investigated from powder x-ray diffraction, thermogravimetric, and magnetic susceptibility measurements, changing the intercalation temperature Ti and the Li content x. Both Li and HMDA have been co-intercalated stably up to x = 2 roughly in a molar ratio of x:y = 2:1. In the case of Ti = 45 °C, it has been found that both Li and HMDA are co-intercalated locally at the edge of FeSe crystals, indicating that both Li and HMDA are hard to diffuse into the inside of FeSe crystals at 45 °C. In the case of Ti = 100 °C, on the other hand, it has been found that both Li and HMDA diffuse into the inside of FeSe crystals, so that Tc tends to increase with increasing x from ˜30 K at x = 1 up to 38 K at x = 2 owing to the increase in the number of electron carriers doped from Li into the FeSe layers.

  12. Definition of bulky disease in early stage Hodgkin lymphoma in computed tomography era: prognostic significance of measurements in the coronal and transverse planes

    Science.gov (United States)

    Kumar, Anita; Burger, Irene A.; Zhang, Zhigang; Drill, Esther N.; Migliacci, Jocelyn C.; Ng, Andrea; LaCasce, Ann; Wall, Darci; Witzig, Thomas E.; Ristow, Kay; Yahalom, Joachim; Moskowitz, Craig H.; Zelenetz, Andrew D.

    2016-01-01

    Disease bulk is an important prognostic factor in early stage Hodgkin lymphoma, but its definition is unclear in the computed tomography era. This retrospective analysis investigated the prognostic significance of bulky disease measured in transverse and coronal planes on computed tomography imaging. Early stage Hodgkin lymphoma patients (n=185) treated with chemotherapy with or without radiotherapy from 2000–2010 were included. The longest diameter of the largest lymph node mass was measured in transverse and coronal axes on pre-treatment imaging. The optimal cut off for disease bulk was maximal diameter greater than 7 cm measured in either the transverse or coronal plane. Thirty patients with maximal transverse diameter of 7 cm or under were found to have bulk in coronal axis. The 4-year overall survival was 96.5% (CI: 93.3%, 100%) and 4-year relapse-free survival was 86.8% (CI: 81.9%, 92.1%) for all patients. Relapse-free survival at four years for bulky patients was 80.5% (CI: 73%, 88.9%) compared to 94.4% (CI: 89.1%, 100%) for non-bulky; Cox HR 4.21 (CI: 1.43, 12.38) (P=0.004). In bulky patients, relapse-free survival was not impacted in patients treated with chemoradiotherapy; however, it was significantly lower in patients treated with chemotherapy alone. In an independent validation cohort of 38 patients treated with chemotherapy alone, patients with bulky disease had an inferior relapse-free survival [at 4 years, 71.1% (CI: 52.1%, 97%) vs. 94.1% (CI: 83.6%, 100%), Cox HR 5.27 (CI: 0.62, 45.16); P=0.09]. Presence of bulky disease on multidimensional computed tomography imaging is a significant prognostic factor in early stage Hodgkin lymphoma. Coronal reformations may be included for routine Hodgkin lymphoma staging evaluation. In future, our definition of disease bulk may be useful in identifying patients who are most appropriate for chemotherapy alone. PMID:27390360

  13. Gas insulated transmission line having low inductance intercalated sheath

    Science.gov (United States)

    Cookson, Alan H.

    1978-01-01

    A gas insulated transmission line including an outer sheath, an inner conductor disposed within the outer sheath, and an insulating gas between the inner conductor and the outer sheath. The outer sheath comprises an insulating tube having first and second ends, and having interior and exterior surfaces. A first electrically conducting foil is secured to the interior surface of the insulating tube, is spirally wound from one tube end to the second tube end, and has a plurality of overlapping turns. A second electrically conducting foil is secured to the exterior surface of the insulating tube, and is spirally wound in the opposite direction from the first electrically conducting foil. By winding the foils in opposite directions, the inductances within the intercalated sheath will cancel each other out.

  14. Water Intercalation for Seamless, Electrically Insulating, and Thermally Transparent Interfaces.

    Science.gov (United States)

    Wang, Yanlei; Xu, Zhiping

    2016-01-27

    The interface between functional nanostructures and host substrates is of pivotal importance in the design of their nanoelectronic applications because it conveys energy and information between the device and environment. We report here an interface-engineering approach to establish a seamless, electrically insulating, while thermally transparent interface between graphene and metal substrates by introducing water intercalation. Molecular dynamics simulations and first-principles calculations are performed to demonstrate this concept of design, showing that the presence of the interfacial water layer helps to unfold wrinkles formed in the graphene membrane, insulate the electronic coupling between graphene and the substrate, and elevate the interfacial thermal conductance. The findings here lay the ground for a new class of nanoelectronic setups through interface engineering, which could lead to significant improvement in the performance of nanodevices, such as the field-effect transistors. PMID:26720217

  15. Morphology and Structure of Amino-fatty Acid Intercalated Montmorillonite

    Science.gov (United States)

    Reyes, Larry; Sumera, Florentino

    2015-04-01

    Natural clays and its modified forms have been studied for their wide range of applications, including polymer-layered silicate, catalysts and adsorbents. For nanocomposite production, montmorillonite (MMT) clays are often modified with organic surfactants to favor its intermixing with the polymer matrix. In the present study, Na+-montmorillonite (Na+-MMT) was subjected to organo-modification with a protonated 12-aminolauric acid (12-ALA). The amount of amino fatty acid surfactants loaded was 25, 50, 100 and 200% the cation exchange capacity (CEC) of Na+-MMT (25CEC-AMMT, 50CEC-AMMT, 100CEC-AMMT and 200CEC-AMMT). Fatty acid-derived surfactants are an attractive resource of intercalating agents for clays due to their renewability and abundance. X-ray diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) were performed to determine the occurrence of intercalation of 12-ALA and their molecular structure in the clay's silicates. XRD analysis revealed that the interlayer spacing between the alumino-silicate layers increased from 1.25 nm to 1.82 nm with increasing ALA content. The amino fatty acid chains were considered to be in a flat monolayer structure at low surfactant loading, and a bilayered to a pseudotrilayered structure at high surfactant loading. On the other hand, FTIR revealed that the alkyl chains adopt a gauche conformation, indicating their disordered state based on their CH2symmetric and asymmetric vibrations. Thermogravimetric analyses (TGA) allows the determination of the moisture and organic content in clays. Here, TGA revealed that the surfactant in the clay was thermally stable, with Td ranging from 353° C to 417° C. The difference in the melting behavior of the pristine amino fatty acids and confined fatty acids in the interlayer galleries of the clay were evaluated by Differential Scanning Calorimerty (DSC). The melting temperatures (Tm) of the amino fatty acid in the clay were initially found to be higher than those of the free

  16. Nanocomposite materials based on polyurethane intercalated into montmorillonite clay

    International Nuclear Information System (INIS)

    Polyurethane organoclay nanocomposites have been synthesized via in situ polymerization method. The organoclay has been prepared by intercalation of diethanolamine or triethanolamine into montmorillonite clay (MMT) through ion exchange process. The syntheses of polyurethane-organoclay hybrids were carried out by swelling the organoclay into different kinds of diols followed by addition of diisocyanate. The nanocomposites with dispersed structure of MMT was obtained as evidence by scanning electron microscope and X-ray diffraction (XRD). The results shows broaden with low intense and shift of the peak characteristic to d001 spacing to smaller 2θ and the MMT is dispersed homogeneously in the polymer matrix. Also, the TGA showed that the nanocomposites have higher decomposition temperature in comparison with the pristine polyurethane

  17. Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation

    Science.gov (United States)

    Zhu, Gaohua; Liu, Jun; Zheng, Qiye; Zhang, Ruigang; Li, Dongyao; Banerjee, Debasish; Cahill, David G.

    2016-01-01

    Thermal conductivity of two-dimensional (2D) materials is of interest for energy storage, nanoelectronics and optoelectronics. Here, we report that the thermal conductivity of molybdenum disulfide can be modified by electrochemical intercalation. We observe distinct behaviour for thin films with vertically aligned basal planes and natural bulk crystals with basal planes aligned parallel to the surface. The thermal conductivity is measured as a function of the degree of lithiation, using time-domain thermoreflectance. The change of thermal conductivity correlates with the lithiation-induced structural and compositional disorder. We further show that the ratio of the in-plane to through-plane thermal conductivity of bulk crystal is enhanced by the disorder. These results suggest that stacking disorder and mixture of phases is an effective mechanism to modify the anisotropic thermal conductivity of 2D materials. PMID:27767030

  18. Dry synthesis of lithium intercalated graphite powders and carbon fibers

    Energy Technology Data Exchange (ETDEWEB)

    Sacci, Robert L [ORNL; Adamczyk, Leslie A [ORNL; Veith, Gabriel M [ORNL; Dudney, Nancy J [ORNL

    2014-01-01

    Herein we describe the direct synthesis of lithium intercalated graphite by heating under vacuum or ball milling under pressurized Ar(g). Both methods allow for stoichometric control of Li-C ratio in batter-grade graphites and carbon fibers prior formation of a solid electrolyte interphase. The products' surface chemistries, as probed by XPS, suggest that LiC6 are extremely reactive with trace amounts of moisture or oxygen. The open circuit potential and SEM data show that the reactivity of the lithiated battery-grade graphite and the carbon fiber can be related to the density of edge/defect sites on the surfaces. Preliminary results of spontaneous SEI formation on Li-graphite in electrolyte are also given.

  19. Many electron correlations in stage-1 graphene intercalation compounds

    Energy Technology Data Exchange (ETDEWEB)

    Acharya, Sidharth, E-mail: AcharyaSidharth19@yahoo.in; Sharma, Raman, E-mail: sramanb70@mailcity.com [Department of Physics Himachal Pradesh University, Shimla, Shimla-171005 (India)

    2015-05-15

    Many electron correlations in stage-1 graphene intercalation compounds (GICs) are studied in generalized-random-phase-approximation. With this approximation, we are able to study short range exchange and correlation effects in GICs. These exchange correlations leads to BCS superconducting states in which one electron correlates with another via its correlation hole to form a stable pair of electrons known as Cooper pair. Cooper pair energies are calculated as the excitations in S(q,ω) following a method similar to exciton energy calculations. Short range effects governing local field correction G(q,ω) are studied for all wave vectors and frequencies. We have found a reasonable agreement between our results and the earlier theoretical results.

  20. Dielectric properties of halloysite and halloysite-formamide intercalate

    Science.gov (United States)

    Adamczyk, M.; Rok, M.; Wolny, A.; Orzechowski, K.

    2014-01-01

    Due to a high increase in electromagnetic pollution, the protection from non-ionizing electromagnetic radiation (EMR) represents an important problem of contemporary environmental science. We are searching for natural materials with the potential for EMR screening. We have discovered that hydro-halloysite has interesting properties as an EMR absorber. Unfortunately, it is a very unstable material. Drying it for even a short period of time leads to the loss of desired properties. In the paper, we have demonstrated that the intercalation of halloysite (the process of introducing guest molecules into the mineral structure) makes it possible to recover the ability to absorb an electromagnetic wave and obtain a promising material for electromagnetic field shielding applications.

  1. Advantages of GPU technology in DFT calculations of intercalated graphene

    Science.gov (United States)

    Pešić, J.; Gajić, R.

    2014-09-01

    Over the past few years, the expansion of general-purpose graphic-processing unit (GPGPU) technology has had a great impact on computational science. GPGPU is the utilization of a graphics-processing unit (GPU) to perform calculations in applications usually handled by the central processing unit (CPU). Use of GPGPUs as a way to increase computational power in the material sciences has significantly decreased computational costs in already highly demanding calculations. A level of the acceleration and parallelization depends on the problem itself. Some problems can benefit from GPU acceleration and parallelization, such as the finite-difference time-domain algorithm (FTDT) and density-functional theory (DFT), while others cannot take advantage of these modern technologies. A number of GPU-supported applications had emerged in the past several years (www.nvidia.com/object/gpu-applications.html). Quantum Espresso (QE) is reported as an integrated suite of open source computer codes for electronic-structure calculations and materials modeling at the nano-scale. It is based on DFT, the use of a plane-waves basis and a pseudopotential approach. Since the QE 5.0 version, it has been implemented as a plug-in component for standard QE packages that allows exploiting the capabilities of Nvidia GPU graphic cards (www.qe-forge.org/gf/proj). In this study, we have examined the impact of the usage of GPU acceleration and parallelization on the numerical performance of DFT calculations. Graphene has been attracting attention worldwide and has already shown some remarkable properties. We have studied an intercalated graphene, using the QE package PHonon, which employs GPU. The term ‘intercalation’ refers to a process whereby foreign adatoms are inserted onto a graphene lattice. In addition, by intercalating different atoms between graphene layers, it is possible to tune their physical properties. Our experiments have shown there are benefits from using GPUs, and we reached an

  2. Organogold reactivity with palladium, nickel, and rhodium: transmetalation, cross-coupling, and dual catalysis.

    Science.gov (United States)

    Hirner, Joshua J; Shi, Yili; Blum, Suzanne A

    2011-08-16

    Using two transition metals to simultaneously catalyze a reaction can offer distinct opportunities for reactivity and selectivity when compared to using single-metal catalyst systems. Creating dual transition metal catalytic systems is complicated, however, by challenges in predicting compatible reactivities and designing turnover pathways for both metals. In this Account, we describe our development of dual-metal catalysis reactions involving gold and a second transition metal. The unique rearrangement intermediates accessible through gold-only catalysis, which exploits the soft Lewis acidity of Au(I), make gold an attractive partner for dual-metal catalysis reactions. Because of the complexity of achieving simultaneous turnover of two catalysts and predicting compatibilities, our approach has been to first gain a fundamental understanding of the reactivity of the two metals with each other, both in stoichiometric and monocatalyzed reactions. To this end, we have investigated the combined reactivity of organogold compounds with palladium, nickel, and rhodium. We narrate the intricacies of turning over two catalysts simultaneously and thereby illuminate the valuable role of fundamental studies in identifying the optimal conditions to promote desirable two-metal reactivity and compatibility. Transmetalation, redox reactivity, and new mechanisms for dual-metal catalytic turnover were probed from this standpoint. We have applied the knowledge gained through these studies to the development of reactions that are dual-catalyzed by gold and palladium, as well as nickel- and rhodium-catalyzed reactions of organogold compounds. More broadly, these new reactions expand the reactivity available to catalytic organogold intermediates via trapping and functionalization reactions with other transition metals. Our investigations reveal strategies useful for designing dual-metal reactions with gold. First, the versatility of gold as a transmetalation partner suggests that many

  3. Strong DNA deformation required for extremely slow DNA threading intercalation by a binuclear ruthenium complex

    Science.gov (United States)

    Almaqwashi, Ali A.; Paramanathan, Thayaparan; Lincoln, Per; Rouzina, Ioulia; Westerlund, Fredrik; Williams, Mark C.

    2014-01-01

    DNA intercalation by threading is expected to yield high affinity and slow dissociation, properties desirable for DNA-targeted therapeutics. To measure these properties, we utilize single molecule DNA stretching to quantify both the binding affinity and the force-dependent threading intercalation kinetics of the binuclear ruthenium complex Δ,Δ-[μ‐bidppz‐(phen)4Ru2]4+ (Δ,Δ-P). We measure the DNA elongation at a range of constant stretching forces using optical tweezers, allowing direct characterization of the intercalation kinetics as well as the amount intercalated at equilibrium. Higher forces exponentially facilitate the intercalative binding, leading to a profound decrease in the binding site size that results in one ligand intercalated at almost every DNA base stack. The zero force Δ,Δ-P intercalation Kd is 44 nM, 25-fold stronger than the analogous mono-nuclear ligand (Δ-P). The force-dependent kinetics analysis reveals a mechanism that requires DNA elongation of 0.33 nm for association, relaxation to an equilibrium elongation of 0.19 nm, and an additional elongation of 0.14 nm from the equilibrium state for dissociation. In cells, a molecule with binding properties similar to Δ,Δ-P may rapidly bind DNA destabilized by enzymes during replication or transcription, but upon enzyme dissociation it is predicted to remain intercalated for several hours, thereby interfering with essential biological processes. PMID:25245944

  4. Synthesis and characterization of montmorillonite clay intercalated with molecular magnetic compounds

    International Nuclear Information System (INIS)

    In this work montmorillonite (MMT) clay, whose matrix was modified with an ammonium salt (hexadecyltrimethylammonium bromide – CTAB), was employed as an inorganic host for the intercalation of three different molecular magnetic compounds through ion exchange: a nitronyl nitroxide derivative 2-[4-(N-ethyl)-pyridinium]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (p-EtRad+) and two binuclear coordination compounds, [Ni(valpn)Ln]3+, where H2valpn stands for 1,3-propanediyl-bis(2-iminomethylene-6-methoxy-phenol), and Ln=GdIII; DyIII. The pristine MMT and the intercalated materials were characterized by X-ray powder diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and magnetic measurements. The X-ray diffraction data analysis showed an increase of the interlamellar space of the intercalated MMT, indicating the intercalation of the magnetic compounds. Furthermore, the magnetic properties of the hybrid compounds were investigated, showing similar behavior as the pure magnetic guest species. - Graphical abstract: Montmorillonite clay was employed as inorganic host for the intercalation of three different molecular magnetic compounds through ion exchange - Highlights: • Montmorillonite was employed as a host material. • Three molecular magnetic compounds were intercalated through ion exchange. • The compounds were successful intercalated maintaining the layered structure. • The hybrid materials exhibited similar magnetic behavior as the pure magnetic guest

  5. Carbon dioxide intercalation in Na-fluorohectorite clay at near-ambient conditions

    Science.gov (United States)

    Fossum, Jon Otto; Hemmen, Henrik; Rolseth, Erlend G.; Fonseca, Davi; Lindbo Hansen, Elisabeth; Plivelic, Tomas

    2012-02-01

    A molecular dynamics study by Cygan et al.[1] shows the possibility of intercalation and retention of CO2 in smectite clays at 37 ^oC and 200 bar, which suggests that clay minerals may prove suitable for carbon capture and carbon dioxide sequestration. In this work we show from x-ray diffraction measurements that gaseous CO2 intercalates into the interlayer space of the synthetic smectite clay Na-fluorohectorite. The mean interlayer distance of the clay when CO2 is intercalated is 12.5 å at -20 C and 15 bar. The magnitude of the expansion of the interlayer upon intercalation is indistinguishable from that of the dehydrated-monohydrated intercalation of H2O, but this possibility is ruled out by careful repeating the measurements exposing the clay to nitrogen gas. The dynamics of the CO2 intercalation process displays a higher intercalation rate at increased pressure, and the rate is several orders of magnitude slower than that of water or vapor at ambient pressure and temperature.[4pt] [1] Cygan, R. T.; Romanov, V. N.; Myshakin, E. M. Natural materials for carbon capture; Techincal report SAND2010-7217; Sandia National Laboratories: Albuquerque, New Mexico, November, 2010.

  6. Thermodynamic Complexing of Monocyclopentadienylferrum (II) Intercalates with Double-Walled Carbon Nanotubes.

    Science.gov (United States)

    Мykhailenko, О V; Prylutskyy, Yu I; Кomarov, І V; Strungar, А V

    2016-12-01

    By employing the methods of molecular mechanics, semi-empirical quantum-chemical РМ3 and Monte-Carlo, the positioning of monocyclopentadienylferrum (II) molecules in double-walled (5,5)@(10,10) carbon nanotubes (CNT) depending on their concentration and temperature has been studied. The molecules have been found out to form stable bonds with CNT walls, with a tendency between intercalate stability and the CNT structure. The temperature growth (over ~500 K) causes gradual bond ruining followed by extrusion of interwall intercalate. Further temperature increase up to 600-700 K is characterised with intercalate external surface desorption, stabilising the whole system and keeping the interwall intercalate only. The CNT's UV-spectrum (5,5)@(10,10) depending on the intercalate concentration and association constant of the "double-walled CNT-intercalate" system have been calculated. A combination of unique optical, electrical and magnetic behaviour of cyclopentadienyl complexes with their ability to form high-stable intercalate with CNT opens a prospect of their applying in nanotechnology. PMID:26951128

  7. Electronic and transmission properties of magnetotunnel junctions of cobalt/iron intercalated bilayer two dimensional sheets

    Energy Technology Data Exchange (ETDEWEB)

    Jiao, N.; Xie, M.D. [Department of Physics, Xiangtan University, Xiangtan 411105, Hunan (China); Zhou, P. [Hunan Provincial Key Laboratory of Thin Film Materials and Devices, School of Materials Science and Engineering, Xiangtan University, Xiangtan 411105 (China); Sun, L.Z., E-mail: lzsun@xtu.edu.cn [Hunan Provincial Key Laboratory of Thin Film Materials and Devices, School of Materials Science and Engineering, Xiangtan University, Xiangtan 411105 (China)

    2015-10-23

    Highlights: • The TMR ratio reaches 169% for Co intercalated Ni|bi-GBN|Ni MTJs. • The TMR ratio reaches 173% for Fe intercalated Ni|bi-GBN|Ni MTJs. • Intercalated Co/Fe effectively modulates the spin filtering of bilayer systems. - Abstract: Density functional theory and the nonequilibrium Green's function method are used to study the electronic properties and tunneling magnetoresistance (TMR) of magnetotunnel junctions (MTJs) based on Co/Fe intercalated bilayer graphene (bi-Gr), bilayer hexagonal boron nitride (bi-h-BN), and bilayer Gr-h-BN (bi-GBN). The spin-polarized bands around the Fermi energy of the two dimensional bilayer sheets are modulated by the intercalated cobalt. The TMR ratio reaches 169.94% and 173.00% for cobalt and iron intercalated Ni|bi-GBN|Ni MTJs, respectively. We observe that the Co/Fe intercalated bi-GBN is a promising candidate as a spacer in MTJs for spintronics.

  8. Synthesis and characterization of montmorillonite clay intercalated with molecular magnetic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Martins, Marcel G.; Martins, Daniel O.T.A.; Carvalho, Beatriz L.C. de [Instituto de Química, Universidade Federal Fluminense, Niterói, RJ 24.020–150 (Brazil); Mercante, Luiza A. [Laboratório Nacional de Nanotecnologia para o Agronegócio (LNNA), Embrapa Instrumentação, São Carlos, SP 13560 970 (Brazil); Soriano, Stéphane [Instituto de Física, Universidade Federal Fluminense, Niterói, RJ 24.210 346 (Brazil); Andruh, Marius [Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str. Dumbrava Rosie nr. 23, Bucharest (Romania); Vieira, Méri D., E-mail: gqimeri@vm.uff.br [Instituto de Química, Universidade Federal Fluminense, Niterói, RJ 24.020–150 (Brazil); Vaz, Maria G.F., E-mail: mariavaz@vm.uff.br [Instituto de Química, Universidade Federal Fluminense, Niterói, RJ 24.020–150 (Brazil)

    2015-08-15

    In this work montmorillonite (MMT) clay, whose matrix was modified with an ammonium salt (hexadecyltrimethylammonium bromide – CTAB), was employed as an inorganic host for the intercalation of three different molecular magnetic compounds through ion exchange: a nitronyl nitroxide derivative 2-[4-(N-ethyl)-pyridinium]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (p-EtRad{sup +}) and two binuclear coordination compounds, [Ni(valpn)Ln]{sup 3+}, where H{sub 2}valpn stands for 1,3-propanediyl-bis(2-iminomethylene-6-methoxy-phenol), and Ln=Gd{sup III}; Dy{sup III}. The pristine MMT and the intercalated materials were characterized by X-ray powder diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and magnetic measurements. The X-ray diffraction data analysis showed an increase of the interlamellar space of the intercalated MMT, indicating the intercalation of the magnetic compounds. Furthermore, the magnetic properties of the hybrid compounds were investigated, showing similar behavior as the pure magnetic guest species. - Graphical abstract: Montmorillonite clay was employed as inorganic host for the intercalation of three different molecular magnetic compounds through ion exchange - Highlights: • Montmorillonite was employed as a host material. • Three molecular magnetic compounds were intercalated through ion exchange. • The compounds were successful intercalated maintaining the layered structure. • The hybrid materials exhibited similar magnetic behavior as the pure magnetic guest.

  9. Single-molecule kinetics and footprinting of DNA bis-intercalation: the paradigmatic case of Thiocoraline.

    Science.gov (United States)

    Camunas-Soler, Joan; Manosas, Maria; Frutos, Silvia; Tulla-Puche, Judit; Albericio, Fernando; Ritort, Felix

    2015-03-11

    DNA bis-intercalators are widely used in molecular biology with applications ranging from DNA imaging to anticancer pharmacology. Two fundamental aspects of these ligands are the lifetime of the bis-intercalated complexes and their sequence selectivity. Here, we perform single-molecule optical tweezers experiments with the peptide Thiocoraline showing, for the first time, that bis-intercalation is driven by a very slow off-rate that steeply decreases with applied force. This feature reveals the existence of a long-lived (minutes) mono-intercalated intermediate that contributes to the extremely long lifetime of the complex (hours). We further exploit this particularly slow kinetics to determine the thermodynamics of binding and persistence length of bis-intercalated DNA for a given fraction of bound ligand, a measurement inaccessible in previous studies of faster intercalating agents. We also develop a novel single-molecule footprinting technique based on DNA unzipping and determine the preferred binding sites of Thiocoraline with one base-pair resolution. This fast and radiolabelling-free footprinting technique provides direct access to the binding sites of small ligands to nucleic acids without the need of cleavage agents. Overall, our results provide new insights into the binding pathway of bis-intercalators and the reported selectivity might be of relevance for this and other anticancer drugs interfering with DNA replication and transcription in carcinogenic cell lines. PMID:25690887

  10. Neutron scattering studies of hydrogen in potassium-graphite intercalates: Towards tunable graphite intercalates for hydrogen storage

    International Nuclear Information System (INIS)

    Low-temperature neutron scattering studies on the ternary graphite intercalation compounds KC24(H2)x, x=1,1.5 show low-energy excitations analogous to those seen in CsC24(H2)x and RbC24(H2)x, attributable to the rotational mode of the H2 split due to the crystal field of the graphene sheets. As in the Cs and Rb-doped systems the hydrogen in KC24(H2)x also occupies two sites. But no preferential population of sites was observed, implying that both sites fill at lower H2 concentration than in the Cs and Rb systems. Increasing c-lattice spacing by doping with deuterated ammonia has the effect of hindering the H2 adsorption, underlining the importance of an optimised graphite-charging regime to maximise hydrogen storage capability in these systems

  11. COPOLYMERIZATION OF CARBON DIOXIDE AND CYCLOHEXENE OXIDE CATALYZED BY ALUMINUM PORPHYRIN-QUATERNARY AMMONIUM SALT IN THE PRESENCE OF BULKY LEWIS ACID

    Institute of Scientific and Technical Information of China (English)

    Yu-sheng Qin; Xian-hong Wang; Xiao-jiang Zhao; Fo-song Wang

    2008-01-01

    Chloro(5,10,15,20-tetraphenyl-porphyrinato)-aluminum/tetraethylammonium bromide (Et4NBr) in combinationwith bulky Lewis acid was used for the copolymerization of CO2 and cyclohexene oxide (CHO). Bulky Lewis acid havingsubstituents at the ortho positions of the phenolate ligands, like methylaluminum bis(2,6-di-tert-butyl-4-methylphenolate),significantly shortened the induction period and raised the catalytic activity, the corresponding turnover frequency reached44.9 h-1 in 9 h, which was 23.8% higher than that from (TPP)AICI/EtaNBr binary catalyst. The resulting polycarbonate hascarbonate linkage over 93% with number average molecular weight of (4.5-6.5)×103 and polydispersity index below 1.10.

  12. Ab initio Calculations of the Formation Energies of Lithium Intercalations in SnSb

    Institute of Scientific and Technical Information of China (English)

    Zhufeng HOU; Aiyu LI; Zizhong ZHU; Meichun HUANG; Yong YANG

    2004-01-01

    SnSb has attracted a great attention in recent investigations as an anode material for Li ion batteries. The formation energies and electronic properties of the Li intercalations in SnSb have been calculated within the framework of local density functional theory and the first-principles pseudopotential technique. The changes of volumes, band structures, charge density analysis and the electronic density of states for the Li intercalations are presented. The results show that the average Li intercalation formation energy per Li atom is around 2.7 eV.

  13. Synthesis of reduced graphene oxide intercalated ZnO quantum dots nanoballs for selective biosensing detection

    Science.gov (United States)

    Chen, Jing; Zhao, Minggang; Li, Yingchun; Fan, Sisi; Ding, Longjiang; Liang, Jingjing; Chen, Shougang

    2016-07-01

    ZnO quantum dots (QDs), reduced graphene oxide (rGO) and multi-walled carbon nanotubes (MWCNTs) are always used in sensors due to their excellent electrochemical characteristics. In this work, ZnO QDs were intercalated by rGO sheets with cross-linked MWCNTs to construct intercalation nanoballs. A MWCNTs/rGO/ZnO QDs 3D hierarchical architecture was fabricated on supporting Ni foam, which exhibited excellent mechanical, kinetic and electrochemical properties. The intercalation construction can introduce strong interfacial effects to improve the surface electronic state. The selectively determinate of uric acid, dopamine, and ascorbic acid by an electrode material using distinct applied potentials was realized.

  14. Synthesis and characterization of laurate-intercalated Mg–Al layered double hydroxide prepared by coprecipitation

    DEFF Research Database (Denmark)

    Gerds, Nathalie Christiane; Katiyar, Vimal; Koch, Christian Bender;

    2012-01-01

    Effective utilization of layered double hydroxides (LDH) for industrial applications requires the synthesis of pure and well-defined LDH phases. In the present study, dodecanoate (laurate) anions were intercalated into Mg–Al-layered double hydroxide (LDH-C12) by coprecipitation in the presence...... intercalated structure, but we here demonstrate it to be magnesium laurate (Mg-C12). The LDH-C12 compound showed high structural order with a basal spacing of 2.41nm. Fourier-transform IR-spectra confirmed the intercalation of the laurate anions in the interlayer. Transmission electron microscopy showed plate...

  15. Room Temperature Ferromagnetism in InTe Layered Semiconductor Crystals Intercalated by Cobalt

    Directory of Open Access Journals (Sweden)

    V.B. Boledzyuk

    2015-03-01

    Full Text Available The magnetic properties of CoxInTe layered crystals electrochemically intercalated with cobalt in constant gradient magnetic field and the morphology of the van der Waals surfaces of layers of these crystals were studied. It was established that impurity clusters consisting of cobalt nanoparticles are formed in the intercalates under investigation on the van der Waals planes in the interlayer space. It was revealed that at room temperature the investigated CoxInTe intercalates exhibit magnetic properties characteristic for magnetically hard ferromagnetic materials.

  16. High voltage and high specific capacity dual intercalating electrode Li-ion batteries

    Science.gov (United States)

    West, William C. (Inventor); Blanco, Mario (Inventor)

    2010-01-01

    The present invention provides high capacity and high voltage Li-ion batteries that have a carbonaceous cathode and a nonaqueous electrolyte solution comprising LiF salt and an anion receptor that binds the fluoride ion. The batteries can comprise dual intercalating electrode Li ion batteries. Methods of the present invention use a cathode and electrode pair, wherein each of the electrodes reversibly intercalate ions provided by a LiF salt to make a high voltage and high specific capacity dual intercalating electrode Li-ion battery. The present methods and systems provide high-capacity batteries particularly useful in powering devices where minimizing battery mass is important.

  17. Stabilization of coordinatively unsaturated Ir4 clusters with bulky ligands: a comparative study of chemical and mechanical effects.

    Science.gov (United States)

    Okrut, Alexander; Gazit, Oz; de Silva, Namal; Nichiporuk, Rita; Solovyov, Andrew; Katz, Alexander

    2012-02-21

    The synthesis and characterization of new cluster compounds represented by the series Ir(4)(CO)(12-x)L(x) (L = tert-butyl-calix[4]-arene(OPr)(3)(OCH(2)PPh(2)); x = 2 and 3) is reported using ESI mass spectrometry, NMR spectroscopy, IR spectroscopy and single-crystal X-ray diffraction. Thermally driven decarbonylation of the cluster compound series represented by x = 1-3 according to the formula above is followed via FTIR and NMR spectroscopies, and dynamic light scattering in toluene solution. The propensity of these clusters to decarbonylate in solution is shown to be directly correlated with number density of adsorbed calixarene phosphine ligands and controlled via Pauli repulsion between metal d and CO 5σ orbitals. The tendency for cluster aggregation unintuitively follows a trend that is exactly opposite to the cluster's propensity to decarbonylate. No cluster aggregation is observed for clusters consisting of x = 3, even after extensive decarbonylation via loss of all bridging CO ligands and coordinative unsaturation. Some of the CO lost during thermal treatment via decarbonylation can be rebound to the coordinatively unsaturated cluster consisting of x = 3. In contrast, the clusters consisting of x = 1 and x = 2 both aggregate into large nanoparticles when treated under identical conditions. Clusters in which the calixarene phosphine ligand is replaced with a sterically less demanding PPh(2)Me ligand 6 lead to significantly less coordinative unsaturation upon thermal treatment. Altogether, these data support a mechanical model of accessibility in coordinatively unsaturated metal clusters in solution, which hinges on having at least three sterically bulky organic ligands per Ir(4) core.

  18. Iridium, platinum and rhodium baseline concentration in lichens from Tierra del Fuego (South Patagonia, Argentina).

    Science.gov (United States)

    Pino, Anna; Alimonti, Alessandro; Conti, Marcelo Enrique; Bocca, Beatrice

    2010-10-01

    Lichen samples of Usnea barbata were used as possible biomonitors of the atmospheric background level of iridium (Ir), platinum (Pt) and rhodium (Rh) in the remote region of Tierra del Fuego (South Patagonia, Argentina). Lichens were collected in 2006 at 53 sites covering 7 different areas of the region (24 transplanted lichens of the northern region and 29 native lichen samples of the central-southern region). A microwave acidic digestion procedure was used to mineralize the samples and a sector field inductively coupled plasma mass spectrometry method was developed to quantify the elements. The study of the influence of interferences on analyte signals and a quality control procedure were carried out. The analytical protocol was further applied to evaluate Ir, Pt and Rh bioaccumulation in lichens. The detection limits obtained were 0.010 ng g⁻¹, 0.013 ng g⁻¹ and 0.030 ng g⁻¹ for Ir, Pt and Rh, respectively. Recoveries at different fortification levels were between 96.3% and 106% and precision was 3.3% on average. The metals concentration (as dry weight) spanned the following ranges: Ir, Tierra del Fuego. Values detected are more likely influenced by the long-range atmospheric transport of these pollutants and, in comparison with densely populated areas in the world, they can represent the baseline for low impacted areas. PMID:20830409

  19. Vapour Phase Hydrogenation of Phenol over Rhodium on SBA-15 and SBA-16

    Directory of Open Access Journals (Sweden)

    Liliana Giraldo

    2014-12-01

    Full Text Available In the present work, mesoporous SBA-15 and SBA-16 were synthesised using classical methods, and their physicochemical properties were investigated by X-ray diffraction (XRD, FTIR, TEM and N2 adsorption–desorption. Rhodium (Rh, 1 wt % was loaded on the mesoporous SBA-15 and SBA-16 by an impregnation method. The Rh surface coverage, dispersion and crystallite size were determined by room temperature H2 chemisorption on reduced samples. The catalytic activity of Rh supported on mesoporous SBA-15 and SBA-16 was evaluated for the first time in the hydrogenation of phenol in vapour phase in a temperature range between 130 and 270 °C at atmospheric pressure. The reaction over Rh/SBA-15 at 180 °C produced cyclohexanone as the major product (about 60% along with lower amounts of cyclohexanol (about 35% and cyclohexane (about 15%. The influences of temperature, H2/phenol ratio, contact time and the nature of the solvent on the catalytic performance were systematically investigated. The Rh/SBA-16 system offered lower phenol conversion compared to Rh/SBA-15, but both have a very high selectivity for cyclohexanone (above 60%.

  20. Nanofiltration of rhodium tris(triphenylphosphine) catalyst in ethyl acetate solution

    Science.gov (United States)

    Shaharun, Maizatul S.; Mustafa, Ahmad K.; Taha, Mohd F.

    2012-09-01

    Solvent resistant nanofiltration (SRNF) using polymer membranes has recently received enhanced attention due to the search for cleaner and more energy-efficient technologies. The large size of the rhodium tris(triphenylphosphine) [HRh(CO)(PPh3)3] catalyst (>400 Da) - relative to other components of the hydroformylation reaction provides the opportunity for a membrane separation based on retention of the catalyst species while permeating the solvent. The compatibility of the solvent-polyimide membrane (DuraMem{trade mark, serif} 200 and DuraMem{trade mark, serif} 500) combinations was assessed in terms of the membrane stability in solvent plus non-zero solvent flux at 2.0 MPa. Good HRh(CO)(PPh3)3 rejection (>0.95) and solvent fluxes of 9.9 L/m2ṡh1 at 2.0 MPa were obtained in the catalyst-ethyl acetate-DuraMem 500 system. The effect of pressure and catalyst concentration on the solvent flux and catalyst rejection was conducted on the catalyst-ethyl acetate-membrane systems. Increasing pressure substantially improved both solvent flux and catalyst rejection, while increasing catalyst concentration was found to be beneficial in terms of substantial increases in catalyst rejection without significantly affecting solvent flux.

  1. Preparation and Structural Investigation of CuCl2 Graphite Intercalation Compounds

    Institute of Scientific and Technical Information of China (English)

    BIN Xiaopei; CHEN Jiazang; CAO Hong; MA Enbao; WANG Xuehua; YUAN Jizhu

    2008-01-01

    Superfine graphite powder was prepared by ball-milling exfoliated graphite containing anhydrous CuCl2 in planetary ball milling systems. Nano-scale CuCl2 graphite intercalation compounds were synthesized by heating a mixture of anhydrous CuCl2 and graphite nanosheets.Scanning electron microscopy, energy-dispersive X-ray spectroscopy and high-resolution transmission electron microscopy were performed to characterize the microstructures of stage-1 nano-scale CuCl2 graphite intercalation compounds. The structure and components of the domain wall and core in thenano-scale CuCl2 graphite intercalation compounds are described. The results show that the contentof CuCl2 in the mixture plays a crucial role in the size of the nano-scale CuCl2 graphite intercalation compound.

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

    Science.gov (United States)

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

    2003-07-28

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

  3. The Benzyl Moiety in a Quinoxaline-Based Scaffold Acts as a DNA Intercalation Switch.

    Science.gov (United States)

    Mahata, Tridib; Kanungo, Ajay; Ganguly, Sudakshina; Modugula, Eswar Kalyan; Choudhury, Susobhan; Pal, Samir Kumar; Basu, Gautam; Dutta, Sanjay

    2016-06-27

    Quinoxaline antibiotics intercalate dsDNA and exhibit antitumor properties. However, they are difficult to synthesize and their structural complexity impedes a clear mechanistic understanding of DNA binding. Therefore design and synthesis of minimal-intercalators, using only part of the antibiotic scaffold so as to retain the key DNA-binding property, is extremely important. Reported is a unique example of a monomeric quinoxaline derivative of a 6-nitroquinoxaline-2,3-diamine scaffold which binds dsDNA by two different modes. While benzyl derivatives bound DNA in a sequential fashion, with intercalation as the second event, nonbenzyl derivatives showed only the first binding event. The benzyl intercalation switch provides important insights about molecular architecture which control specific DNA binding modes and would be useful in designing functionally important monomeric quinoxaline DNA binders and benchmarking molecular simulations.

  4. Optimization of the Thermoelectric Figure of Merit in Crystalline C60 with Intercalation Chemistry.

    Science.gov (United States)

    Kim, Jeong Yun; Grossman, Jeffrey C

    2016-07-13

    Crystalline C60 is an appealing candidate material for thermoelectric (TE) applications due to its extremely low thermal conductivity and potentially high electrical conductivity with metal atom intercalation. We investigate the TE properties of crystalline C60 intercalated with alkali and alkaline earth metals using both classical and quantum mechanical calculations. For the electronic structure, our results show that variation of intercalated metal atoms has a large impact on energy dispersions, which leads to broad tunability of the power factor. For the thermal transport, we show that dopants introduce strong phonon scattering into crystalline C60, leading to considerably lower thermal conductivity. Taking both into account, our calculations suggest that appropriate choice of metal atom intercalation in crystalline C60 could yield figures of merit near 1 at room temperature.

  5. Optimization of the Thermoelectric Figure of Merit in Crystalline C60 with Intercalation Chemistry.

    Science.gov (United States)

    Kim, Jeong Yun; Grossman, Jeffrey C

    2016-07-13

    Crystalline C60 is an appealing candidate material for thermoelectric (TE) applications due to its extremely low thermal conductivity and potentially high electrical conductivity with metal atom intercalation. We investigate the TE properties of crystalline C60 intercalated with alkali and alkaline earth metals using both classical and quantum mechanical calculations. For the electronic structure, our results show that variation of intercalated metal atoms has a large impact on energy dispersions, which leads to broad tunability of the power factor. For the thermal transport, we show that dopants introduce strong phonon scattering into crystalline C60, leading to considerably lower thermal conductivity. Taking both into account, our calculations suggest that appropriate choice of metal atom intercalation in crystalline C60 could yield figures of merit near 1 at room temperature. PMID:27322341

  6. Synthesis, Structural Characterization of TTM-TTF Intercalated with Lamellar MnPS3

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xuan; CHEN Xing-Guo; FU Yang; SU Xu; QIN Jin-Gui

    2003-01-01

    @@ Intercalation of organic species into layer inorganic solids provides a useful approach to creating ordered organ ic-inorganic nanocomposite materials with novel properties compared with the parent compounds, and hence has attracted much attention in recent years. [1] Clement and co-workers had reported that an organic electron donor TTF monocation intercalated into the MPS3 (M = Mn, Fe), and the intercalates exhibited much higher conductivity than the corresponding pure host compounds. Our group also synthesized the intercalation compound of BEDT-TTF into MnPS3, which exhibits the room temperature conductivity of 8.5 × 10-5 S/cm, 1O5 times higher than that of the pristine MnPS3 ( < 10- 10 S/cm). [2

  7. Oxygen intercalation under graphene on Ir(111): energetics, kinetics, and the role of graphene edges.

    Science.gov (United States)

    Grånäs, Elin; Knudsen, Jan; Schröder, Ulrike A; Gerber, Timm; Busse, Carsten; Arman, Mohammad A; Schulte, Karina; Andersen, Jesper N; Michely, Thomas

    2012-11-27

    Using X-ray photoemission spectroscopy (XPS) and scanning tunneling microscopy (STM) we resolve the temperature-, time-, and flake size-dependent intercalation phases of oxygen underneath graphene on Ir(111) formed upon exposure to molecular oxygen. Through the applied pressure of molecular oxygen the atomic oxygen created on the bare Ir terraces is driven underneath graphene flakes. The importance of substrate steps and of the unbinding of graphene flake edges from the substrate for the intercalation is identified. With the use of CO titration to selectively remove oxygen from the bare Ir terraces the energetics of intercalation is uncovered. Cluster decoration techniques are used as an efficient tool to visualize intercalation processes in real space.

  8. CO intercalation of graphene on Ir(111) in the millibar regime

    DEFF Research Database (Denmark)

    Arman, M.A.; Andersen, Mie; Granas, E.;

    2013-01-01

    characterize nonintercalated stripes and islands that we always observe in the CO-intercalated graphene. We observe these nonintercalated areas predominately in HCP and FCC areas near step edges and suggest that stress release in graphene is the driving force for their formation, while the weak chemical bonds......Here we show that it is possible to intercalate CO under graphene grown on Ir(111) already at room temperature when CO pressures in the millibar regime are used. From the interplay of X-ray photoelectron spectroscopy and scanning tunneling microscopy we conclude that the intercalated CO adsorption...... structure is similar to the (3√3 × 3√3)R30°) adsorption structure that is formed on Ir(111) upon exposure to 1 mbar of CO. Further, density functional theory calculations reveal that the structural and electronic properties of CO-intercalated graphene are similar to p-doped freestanding graphene. Finally we...

  9. Preparation of association compound between rhodium(II) citrate and {beta}-cyclodextrin; Preparacao do composto de associacao entre citrato de rodio(II) e {beta}-ciclodextrina

    Energy Technology Data Exchange (ETDEWEB)

    Burgos, Ana E.; Okio, Coco K.Y.A., E-mail: aeburgosc@unal.edu.co [Departamento de Quimica, Universidad Nacional de Colombia, Bogota (Colombia); Sinisterra, Ruben D. [Departamento de Quimica, Instituto de Ciencias Exatas, Universidade Federal de Minas Gerais, Belo Horizonte - MG (Brazil)

    2012-07-01

    Inclusion compound of rhodium(II) citrate with{beta}-cyclodextrin in a 1:1 molar ratio was prepared using freeze-drying method. X-ray diffractometry, thermal analysis (TG/DTG/DSC), infrared and {sup 1}H-NMR with {sup 1}H spin lattice relaxation ({sup 1}H T{sub 1}) measurements and {sup 13}C techniques were used to characterize the system prepared. The results indicated the formation of inclusion or association compounds between rhodium(II) citrate and {beta}-cyclodextrin. (author)

  10. An insight on the weakening of the interlayer bonds in a Cameroonian kaolinite through DMSO intercalation

    OpenAIRE

    Mbey, Jean-Aimé; Thomas, Fabien; NGALLY-SABOUANG, Cyrill-Joel; LIBOUM, François; Njopwouo, Daniel

    2013-01-01

    In this study, intercalation of dimethylsulphoxide (DMSO) in a Cameroonian kaolinite is used to achieve weakening of the interlayer hydrogen bonds, in the perspective of dispersion or even exfoliation of the clay within polymer composite materials. Displacement of intercalated DMSO by ethyl acetate and ammonium acetate is studied in order to simulate the interactions with the polymer matrix. The exfoliation of the kaolinite is well evidenced by X-ray diffraction and SEM observations. The disr...

  11. Recent Developments in the Chemistry of Deoxyribonucleic Acid (DNA Intercalators: Principles, Design, Synthesis, Applications and Trends

    Directory of Open Access Journals (Sweden)

    Alexandre A. M. Lapis

    2009-05-01

    Full Text Available In the present overview, we describe the bases of intercalation of small molecules (cationic and polar neutral compounds in DNA. We briefly describe the importance of DNA structure and principles of intercalation. Selected syntheses, possibilities and applications are shown to exemplify the importance, drawbacks and challenges in this pertinent, new, and exciting research area. Additionally, some clinical applications (molecular processes, cancer therapy and others and trends are described.

  12. Effect of the intercalated cation on the properties of poly(o-methylaniline)/maghnite clay nanocomposites

    OpenAIRE

    Salavagione, Horacio Javier; Cazorla Amorós, Diego; Tidjane, Selma; BELBACHIR Mohammed; Benyoucef, Abdelghani; Morallón Núñez, Emilia

    2007-01-01

    A detailed study about the synthesis, characterization and properties of poly(o-methylaniline)(PoMea)/maghnite nanocomposites has been performed. Changes in the characteristics of the nanocomposites, depending on the intercalated cation between the clay layers before the synthesis, have been observed. Intercalated morphology has been detected by TEM in nanocomposites containing copper-treated maghnite (Magh-Cu), while when maghnite treated with strong acids was used (Magh-H); an e...

  13. Optimal design of parallel triplex forming oligonucleotides containing Twisted Intercalating Nucleic Acids—TINA

    OpenAIRE

    Schneider, Uffe V.; Mikkelsen, Nikolaj D.; Jøhnk, Nina; Okkels, Limei M.; Westh, Henrik; Lisby, Gorm

    2010-01-01

    Twisted intercalating nucleic acid (TINA) is a novel intercalator and stabilizer of Hoogsteen type parallel triplex formations (PT). Specific design rules for position of TINA in triplex forming oligonucleotides (TFOs) have not previously been presented. We describe a complete collection of easy and robust design rules based upon more than 2500 melting points (T m) determined by FRET. To increase the sensitivity of PT, multiple TINAs should be placed with at least 3 nt in-between or preferabl...

  14. Electrochemical potential of intercalation phase: Li/V 2O 5 system

    Science.gov (United States)

    Wu, Qi-Hui

    2006-12-01

    In the communication, the use of photoelectron spectroscopy in evaluating the electrochemical potentials for intercalation phase (Li/V 2O 5 system) is presented. Two contributions, i.e. Fermi level shift and formation of surface dipole, are the main factors in the change of battery voltage during the Li intercalation. It was found that the formation of surface dipole plays more important role in the decrease of the battery voltage due to the adsorption of Li on the surface.

  15. Intercalation of urea into kaolinite for preparation of controlled release fertilizer

    OpenAIRE

    Mahdavi Fariba; Abdul Rashid Suraya; Khanif Yusop Mohd

    2014-01-01

    In this study urea was intercalated between layers of kaolinite by dry grinding technique to be used for preparing controlled release fertilizer. X-ray powder diffraction (XRPD) patterns confirmed the intercalation of urea into kaolinite by the significant expansion of the basal spacing of kaolinite layers from 0.710 nm to 1.090 nm. Fourier transform infrared spectroscopy (FT-IR) also confirmed the hydrogen bonding between urea and kaolinite. Based on CHNS ...

  16. Structural, energetic and electronic properties of intercalated boron–nitride nanotubes

    Indian Academy of Sciences (India)

    S Rada; M Rada; E Culea

    2013-04-01

    The effects of chirality and the intercalation of transitional metal atoms inside single walled BN nanotubes on structural, energetic and electronic properties have been considered in this paper. The thermodynamic stability of BN nanotubes can be improved by the intercalation of cobalt or nickel. BN nanotubes can behave like an ideal non-interacting hosts for these one-dimensional chains of metal atoms. Their electronic properties are insignificantly modified.

  17. Intercalation and De-intercalation of a Dual Phenoxy herbicides into Zn-Al-Layered Double Hydroxide Effect of Anionic Size

    International Nuclear Information System (INIS)

    Agrochemicals, in particular herbicides such as 4-(2,4- dichlorophenoxy)butyrate (DPBA) and 2-(3- chlorophenoxy)propionate (CPPA) have been intercalated simultaneously into Zn/ Al-LDH by direct co-precipitation method to form a new nano hybrid material labeled as NCDD. XRD and UV-Visible spectroscopy results show that the intercalation and release of the dual herbicides are influenced by the anion size. These results will be useful as the starting point to develop tunable controlled release property. (author)

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

    Science.gov (United States)

    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.

  19. Intercalation of acrylic acid and sodium acrylate into kaolinite and their in situ polymerization

    Science.gov (United States)

    Zhang, Bo; Li, Yanfeng; Pan, Xiaobing; Jia, Xin; Wang, Xiaolong

    2007-02-01

    Novel nano-composites of poly (acrylic acid)-kaolinite were prepared, and intercalation and in situ polymerization were used in this process. The nano-composites were obtained by in situ polymerization of acrylic acid (AA) and sodium acrylate (AANa) intercalated into organo-kaolinite, which was obtained by refining and chemically modifying with solution intercalation step in order to increase the basal plane distance of the original clay. The modification was completed by using dimethyl-sulfoxide (DMSO)/methanol and potassium acetate (KAc)/water systems step by step. The materials were characterized with the help of XRD, FT-IR and TEM; the results confirmed that poly(acrylic acid) (PAA) and poly(sodium acrylate) (PAANa) were intercalated into the interlamellar spaces of kaolinite, the resulting copolymer composites (CC0 : copolymer crude kaolinite composite, CC1 : copolymer DMSO kaolinite composite, CC2 : copolymer KAc kaolinite composite) of CC2 exhibited a lamellar nano-composite with a mixed nano-morphology, and partial exfoliation of the intercalating clay platelets should be the main morphology. Finally, the effect of neutralization degree on the intercalation behavior was also investigated.

  20. In situ intercalation dynamics in inorganic-organic layered perovskite thin films.

    Science.gov (United States)

    Ahmad, Shahab; Kanaujia, Pawan K; Niu, Wendy; Baumberg, Jeremy J; Vijaya Prakash, G

    2014-07-01

    The properties of layered inorganic semiconductors can be manipulated by the insertion of foreign molecular species via a process known as intercalation. In the present study, we investigate the phenomenon of organic moiety (R-NH3I) intercalation in layered metal-halide (PbI2)-based inorganic semiconductors, leading to the formation of inorganic-organic (IO) perovskites [(R-NH3)2PbI4]. During this intercalation strong resonant exciton optical transitions are created, enabling study of the dynamics of this process. Simultaneous in situ photoluminescence (PL) and transmission measurements are used to track the structural and exciton evolution. On the basis of the experimental observations, a model is proposed which explains the process of IO perovskite formation during intercalation of the organic moiety through the inorganic semiconductor layers. The interplay between precursor film thickness and organic solution concentration/solvent highlights the role of van der Waals interactions between the layers, as well as the need for maintaining stoichiometry during intercalation. Nucleation and growth occurring during intercalation matches a Johnson-Mehl-Avrami-Kolmogorov model, with results fitting both ideal and nonideal cases. PMID:24905435

  1. In Situ Intercalation Dynamics in Inorganic–Organic Layered Perovskite Thin Films

    Science.gov (United States)

    2014-01-01

    The properties of layered inorganic semiconductors can be manipulated by the insertion of foreign molecular species via a process known as intercalation. In the present study, we investigate the phenomenon of organic moiety (R-NH3I) intercalation in layered metal-halide (PbI2)-based inorganic semiconductors, leading to the formation of inorganic–organic (IO) perovskites [(R-NH3)2PbI4]. During this intercalation strong resonant exciton optical transitions are created, enabling study of the dynamics of this process. Simultaneous in situ photoluminescence (PL) and transmission measurements are used to track the structural and exciton evolution. On the basis of the experimental observations, a model is proposed which explains the process of IO perovskite formation during intercalation of the organic moiety through the inorganic semiconductor layers. The interplay between precursor film thickness and organic solution concentration/solvent highlights the role of van der Waals interactions between the layers, as well as the need for maintaining stoichiometry during intercalation. Nucleation and growth occurring during intercalation matches a Johnson–Mehl–Avrami–Kolmogorov model, with results fitting both ideal and nonideal cases. PMID:24905435

  2. Intercalation and Distribution of Silver in the Transition Metal Dichalcogenide 1T-TITANIUM-DISULFIDE.

    Science.gov (United States)

    Kaluarachchi, Dayakanthi

    The intercalation and motion of silver (Ag) in partially intercalated titanium disulphide (TiS _{rm 2}) crystals were studied using a scanning Auger electron microscope with ion sputtering, a scanning electron microscope with an x-ray fluorescence attachment, an optical microscope and radioactive tracers. The x-ray fluorescence results indicated a rapid conversion of stage 1 Ag into stage 2 Ag at room temperature and a stationary behavior of the stage 2 Ag after the stage conversion was completed. The radioactive tracer results showed that stage 2 Ag was mobile during the stage 1 to stage 2 conversion and also when a crystal was being intercalated. The motion of stage 2 Ag in the bulk of a crystal was observed only when stage 1 was present in the crystal. Auger analysis with ion sputtering yielded the 3-dimensional distribution of Ag in a partially intercalated stage 2 crystal. Ag was observed to be intercalated across the crystal surface region while the bulk was intercalated only for a short distance, indicating that the Ag has a high rate of motion near the crystal surface. A stage 2 region with a high Ag concentration was observed to be unstable near the crystal surface.

  3. Optical properties of NbCl5 and ZnMg intercalated graphite compounds

    Science.gov (United States)

    Jung, Eilho; Lee, Seokbae; Roh, Seulki; Meng, Xiuqing; Tongay, Sefaattin; Kang, Jihoon; Park, Tuson; Hwang, Jungseek

    2014-12-01

    We studied NbCl5 and ZnMg alloy intercalated graphite compounds using an optical spectroscopy technique. These intercalated metallic graphite samples were quite challenging to obtain optical reflectance spectra since they were not flat and quite thin. By using both a new method and an in situ gold evaporation technique we were able to obtain reliable reflectance spectra of our samples in the far and mid infrared range (80-7000 cm-1). We extracted the optical constants including the optical conductivity and the dielectric function from the measured reflectance spectra using a Kramers-Kronig analysis. We also extracted the dc conductivity and the plasma frequencies from the optical conductivity and dielectric functions. NbCl5 intercalated graphite samples show similar optical conductivity spectra as bare highly oriented pyrolytic graphite even though there are some differences in detail. ZnMg intercalated samples show significantly different optical conductivity spectra from the bare graphite. Optical spectroscopy is one of the most reliable experimental techniques to obtain the electronic band structures of materials. The obtained optical conductivities support the recent theoretically calculated electronic band structures of NbCl5 and ZnMg intercalated graphite compounds. Our results also provide important information of electronic structures and charge carrier properties of these two new intercalated materials for applications.

  4. Intramolecular substitutions of square planar rhodium(Ⅰ) catioriic complexes of ds-dicarbonyl nitrogen coordinated tridentate

    Institute of Scientific and Technical Information of China (English)

    袁国卿; 柳忠阳; 朱长城; 潘平来; 刘世宏

    1997-01-01

    Four kinds of square planar cis-dicarbonyl-N,N-bis(2-pyridylethyl)-p-substituted-phenylamino rhodium(Ⅰ) are reported.The changes of their structures were analyzed by XPS,IR and NMR spectroscopy The results show that the weak N→Rh coordinated bond can replace very soon the strong Rh-Cπ back donation bond to form tris-nitrogen coordinated complexes due to the steric effect when the temperature is over 50℃,This reaction is reversible.The bis-nitrogen coordinated structure of the complex recovered when put under the atmosphere of CO

  5. AB INITIO STUDY OF CHEMICAL ACTIVATION AND HYDROGENATION OF WHITE PHOSPHORUS IN REACTION WITH RHODIUM TRIHYDRIDE COMPLEX

    OpenAIRE

    Iolanta I. Balan; Natalia N. Gorinchoy

    2011-01-01

    The four-stage mechanism of reaction of the rhodium trihydride complex [(triphos)RhH3] (triphos=1,1,1-tris(diphenylphosphanylmethyl)ethane) with the white phosphorus molecule resulting in the phosphane and the cyclo-P3 complex [(triphos)M(η3-P3] is analyzed on the basis of ab initio calculations of reactants, products, and intermediate complexes of reaction. It is shown that generation of the transient complex [(triphos)RhH(η1:η1-P4)] followed by intramolecular hydrogen atom migration from t...

  6. Half-sandwich iridium- and rhodium-based organometallic architectures: rational design, synthesis, characterization, and applications.

    Science.gov (United States)

    Han, Ying-Feng; Jin, Guo-Xin

    2014-12-16

    CONSPECTUS: Over the last two decades, researchers have focused on the design and synthesis of supramolecular coordination complexes, which contain discrete functional structures with particular shapes and sizes, and are similar to classic metal-organic frameworks. Chemists can regulate many of these systems by judiciously choosing the metal centers and their adjoining ligands. These resulting complexes have unusual properties and therefore many applications, including molecular recognition, supramolecular catalysis, and some applications as nanomaterials. In addition, researchers have extensively developed synthetic methodologies for the construction of discrete self-assemblies. One of the most important challenges for scientists in this area is to be able to synthesize target structures that can be controlled in both length and width. For this reason, it is important that we understand the factors leading to special shapes and sizes of such architectures, especially how starting building blocks and functional ligands affect the final conformations and cavity sizes of the resulting assemblies. Towards this goal, we have developed a wide range of different organometallic architectures by rationally designing metal-containing precursors and organic ligands. In this Account, we present our recent work, focusing on half-sandwich iridium- and rhodium-based organometallic assemblies that we obtained through rational design. We discuss their synthesis, structures, and applications for the encapsulation of guests and enzyme-mimicking catalysis. We first describe a series of self-assembled organometallic metallarectangles and metallacages, which we constructed from preorganized dinuclear half-sandwich molecular clips and suitable pyridyl ligands. We extended this strategy to tune the size of the obtained rectangles, creating large cavities by introduction of larger molecular clips. The cavity was found to exhibit selective and reversible CH2Cl2 adsorption properties while

  7. Structural sensitivity studies of ethylene hydrogenation on platinum and rhodium surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Quinlan, M.A. [California Univ., Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley National Lab., CA (United States)

    1996-01-01

    The catalytic hydrogenation of ethylene and hydrogen on the well characterized surfaces of the noble metals platinum and rhodium has been studied for the purposes of determining the relative activity of these two substrates as well as the degree of structure sensitivity. The Pt(111) and the Rh(755) single crystal surfaces,as well as Pt and Rh foils, were employed as substrates to study the effect of surface step structure on reactivity. In addition, vibrational spectroscopy studies were performed for ethylene adsorption on the stepped Rh(755) surface. The catalytic reaction were obtained using a combined ultrahigh vacuum chamber coupled with an atmospheric pressure reaction chamber that functioned as a batch reactor. Samples could be prepared using standard surface science techniques and characterized for surface composition and geometry using Auger Electron Spectroscopy and Low Energy Electron Diffraction. A comparison of the reactivity of Rh(111) with the results from this study on Rh(755) allows a direct determination of the effect of step structure on ethylene hydrogenation activity. Structure sensitivity is expected to exhibit orders of magnitude differences in rate as surface orientation is varied. In this case, no significant differences were found, confirming the structure insensitivity of this reaction over this metal. The turnover frequency of the Rh(111) surface, 5 {times} 10{sup 1} s{sup {minus}1}, is in relatively good agreement with the turnover frequency of 9 {times} 10{sup 1} s{sup {minus}1} measured for the Rh(755) surface. Rate measurements made on the Pt(111) surface and the Pt foil are in excellent agreement, both measuring 3 {times} 10{sup 2} s{sup minus}1. Likewise, it is concluded that no strong structure sensitivity for the platinum surfaces exists. High Resolution Electron Energy Loss Spectroscopy studies of adsorbed ethylene on the Rh(755) surface compare favorably with the ethylidyne spectra obtained on the Rh(111) and Rh(100) surfaces.

  8. Hydrogenation of CO and CO2 over rhodium catalysts supported on various metal oxides

    International Nuclear Information System (INIS)

    The formation of hydrocarbons in the reaction of CO + H2 and CO2 + H2 was studied over rhodium catalysts supported on ZrO2, Al2O3, SiO2, and MgO. Among those catalysts, Rh on ZrO2 was most active and Rh-MgO was least active for the above reactions. Over Rh-ZrO2, the CO2 + H2 reaction took place even at 500C, whereas the CO + H2 reaction occurred only at temperature higher than 1300C. The reaction of CO2 + H2 produced only methane at temperatures up to 2000C, but a small amount of CO formed along with methane in the reverse water gas shift reaction above 2000C. In the case of the CO + H2 reaction, the higher molecular weight hydrocarbons (C2 approx. C4) as well as CH4 formed. The inverse kinetic isotope effect was observed in both reactions of CO + H2(D2) and CO2 + H2(D2) over Rh-ZrO2. However, the isotope effect was not observed in the CO2 + H2(D2) reaction over Rh-Al2O3 whose effect in the CO + H2 reaction was still inverse. The activity for the CO + H2 reaction over the oxidized Rh-ZrO2 and Rh-Al2O3 was almost 2 to 10 times higher than that on the reduced catalyst. The reaction mechanisms of the above reactions are discussed. 2 figures, 4 tables

  9. Phosphaalkene-oxazoline copolymers with styrene as chiral ligands for rhodium(I).

    Science.gov (United States)

    Serin, Spencer C; Dake, Gregory R; Gates, Derek P

    2016-04-01

    The radical-initiated copolymerization of phosphaalkene-oxazoline, MesP[double bond, length as m-dash]C(Ph)CMe2Ox [1, Ox = CNOCH(iPr)CH2] with different loadings of styrene affords poly(methylenephosphine-co-styrene)s [2a (1 : S = 1 : 2): Mw = 7400 g mol(-1), PDI = 1.1; 2b (1 : S = 1 : 5): Mw = 18 000 g mol(-1), PDI = 1.2; 2c (1 : S = 1 : 10): Mw = 16 000 g mol(-1), PDI = 1.3]. Copolymers 2a-2c are demonstrated as viable macromolecular ligands for rhodium(i). By comparison with the crystallographically characterized model P,N-bidentate complex, [Mes(Me)P-CH(Ph)CMe2Ox·Rh(cod)]BF4, the polymer complexes [2·Rh(cod)]BF4 were prepared. The macromolecular metal complexes were characterized by GPC {for [2a·Rh(cod)]BF4: Mw = 14 000 g mol(-1), PDI = 1.2}, UV/Vis spectroscopy, (1)H, (13)C and (31)P NMR spectroscopy. Integration of the (31)P NMR spectra of mixtures of 2 and [Rh(cod)2]BF4 permitted the determination of the mol% of incorporation of monomer 1 in copolymer 2 (2a: 17%; 2b: 5%; 2c: 4%). These results compared favorably with those determined by elemental analysis (2a: 17%; 2b: 6%). PMID:26924506

  10. 从合成三(三苯基膦)氯化铑产生的有机废液中回收铑%Recovery of Rhodium from Organic Waste Liquid Produced from the Synthesis of Chlorotri (triphenylphosphine) rhodium

    Institute of Scientific and Technical Information of China (English)

    刘桂华; 侯文明; 沈善问; 周严; 匡飞平; 冯洋洋; 许明明; 潘再富

    2011-01-01

    针对三(三苯基膦)氯化铑合成过程中产生的含铑有机废液的特点,采用火-湿联用工艺成功回收废液中的铑,回收率约达99%.该工艺的主要工序包括:蒸馏回收乙醇和除去水分、焚烧灰化、氯化、净化、氢还原,最终获得纯铑粉.%A process to recover Rh from organic waste solution by pyrometallurgy - hydrometallurgy method was developed. It consists of; (1) evaporation of ethanol and water from the Rh - containing waste solution yielding a solid mixture; ( 2 ) combustion of triphenylphosphine; ( 3 ) chlorination of the resulting residue to convert rhodium into the solution; (4 ) purification by hydrolysis and ion - exchange; and (5) precipitation by reduction with hydrogen, producing pure rhodium powder. The overall recovery rate was up to 99%.

  11. Resistivity features in intercalated graphite compounds with bromine and iodine chloride in the region of structural phase transitions in the layer of intercalate

    International Nuclear Information System (INIS)

    In the paper anomalous changes of resistivity in graphite intercalated compounds with iodine chloride and bromine are investigated in the phase transition temperature interval. It is shown that these anomalies are caused by the change of carriers mobility in the phase transitional interval as well as by the origin of ''mobile ions liquids''

  12. Study of activation cross-sections of deuteron induced reactions on rhodium up to 40 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Ditroi, F., E-mail: ditroi@atomki.hu [Institute of Nuclear Research of the Hungarian Academy of Sciences (ATOMKI), Debrecen (Hungary); Tarkanyi, F.; Takacs, S. [Institute of Nuclear Research of the Hungarian Academy of Sciences (ATOMKI), Debrecen (Hungary); Hermanne, A. [Cyclotron Laboratory, Vrije Universiteit Brussel (VUB), Brussels (Belgium); Yamazaki, H.; Baba, M.; Mohammadi, A. [Cyclotron Radioisotope Center (CYRIC) Tohoku University, Sendai (Japan); Ignatyuk, A.V. [Institute of Physics and Power Engineering (IPPE), Obninsk (Russian Federation)

    2011-09-15

    Highlights: {yields} Excitation function measurement of deuteron induced reactions on rhodium up to 40 MeV. {yields} Model code calculations with EMPIRE, ALICE and TALYS. {yields} Integral production yield calculation. {yields} Thin layer activation (TLA) with the produced isotopes. - Abstract: In the frame of a systematic study of the activation cross-sections of deuteron induced nuclear reactions, excitation functions of the {sup 103}Rh(d,x) {sup 100,101,103}Pd, {sup 100g,101m,101g,102m,102g}Rh and {sup 103g}Ru reactions were determined up to 40 MeV. Cross-sections were measured with the activation method using a stacked foil irradiation technique. Excitation functions of the contributing reactions were calculated using the ALICE-IPPE, EMPIRE-II and TALYS codes. From the measured cross-section data integral production yields were calculated and compared with experimental integral yield data reported in the literature. From the measured cross-sections and previous data, activation curves were deduced to support thin layer activation (TLA) on rhodium and Rh containing alloys.

  13. Long-Term Testing of Rhodium-Based Catalysts for Mixed Alcohol Synthesis – 2013 Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Mark A.; Gray, Michel J.; Thompson, Becky L.

    2013-09-23

    The U.S. Department of Energy’s Pacific Northwest National Laboratory has been conducting research since 2005 to develop a catalyst for the conversion of synthesis gas (carbon monoxide and hydrogen) into mixed alcohols for use in liquid transportation fuels. Initially, research involved screening possible catalysts based on a review of the literature, because at that time, there were no commercial catalysts available. The screening effort resulted in a decision to focus on catalysts containing rhodium and manganese. Subsequent research identified iridium as a key promoter for this catalyst system. Since then, research has continued to improve rhodium/manganese/iridium-based catalysts, optimizing the relative and total concentrations of the three metals, examining baseline catalysts on alternative supports, and examining effects of additional promoters. Testing was continued in FY 2013 to evaluate the performance and long-term stability of the best catalysts tested to date. Three tests were conducted. A long-term test of over 2300 hr duration at a single set of operating conditions was conducted with the best carbon-supported catalyst. A second test of about 650 hr duration at a single set of operating conditions was performed for comparison using the same catalyst formulation on an alternative carbon support. A third test of about 680 hr duration at a single set of operating conditions was performed using the best silica-supported catalyst tested to date.

  14. An operando FTIR spectroscopic and kinetic study of carbon monoxide pressure influence on rhodium-catalyzed olefin hydroformylation.

    Science.gov (United States)

    Kubis, Christoph; Sawall, Mathias; Block, Axel; Neymeyr, Klaus; Ludwig, Ralf; Börner, Armin; Selent, Detlef

    2014-09-01

    The influence of carbon monoxide concentration on the kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a phosphite-modified rhodium catalyst has been studied for the pressure range p(CO)=0.20-3.83 MPa. Highly resolved time-dependent concentration profiles of the organometallic intermediates were derived from IR spectroscopic data collected in situ for the entire olefin-conversion range. The dynamics of the catalyst and organic components are described by enzyme-type kinetics with competitive and uncompetitive inhibition reactions involving carbon monoxide taken into account. Saturation of the alkyl-rhodium intermediates with carbon monoxide as a cosubstrate occurs between 1.5 and 2 MPa of carbon monoxide pressure, which brings about a convergence of aldehyde regioselectivity. Hydrogenolysis of the acyl intermediate is fast at 30 °C and low pressure of p(CO)=0.2 MPa, but is of minus first order with respect to the solution concentration of carbon monoxide. Resting 18-electron hydrido and acyl complexes that correspond to early and late rate-determining states, respectively, coexist as long as the conversion of the substrate is not complete. PMID:25081298

  15. Rhodium-catalyzed selective[2+2+2]cyclizations of 1,6-diynes with monoynes leading to isoindolines and isobenzofurans

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.

  16. Synthesis of solution-phase phosphoramidite and phosphite ligand libraries and their in situ screening in the rhodium-catalyzed asymmetric addition of arylboronic acids

    NARCIS (Netherlands)

    Jagt, Richard B. C.; Toullec, Patrick Y.; Schudde, Ebe P.; de Vries, Johannes G.; Feringa, Ben L.; Minnaard, Adriaan J.

    2007-01-01

    Herein, we report the automated parallel synthesis of solution-phase libraries of phosphoramidite ligands for the development of enantioselective catalysts. The ligand libraries are screened in situ in the asymmetric rhodium-catalyzed addition of arylboronic acids to aldehydes and imines. It is show

  17. Bulky Early-Stage Cervical Cancer (2-4 cm Lesions): Upfront Radical Trachelectomy or Neoadjuvant Chemotherapy Followed by Fertility-Preserving Surgery: Which Is the Best Option?

    Science.gov (United States)

    Plante, Marie

    2015-05-01

    Radical trachelectomy is now recognized as a valid treatment option for young women with early-stage cervical cancer with lesions measuring less than 2 cm. However, for women with bulky lesions measuring greater than 2 cm, few data are available in the literature to guide management. There are currently 2 options available: either upfront radical trachelectomy or neoadjuvant chemotherapy followed by fertility-preserving surgery. Overall, both options offer very good oncologic outcome; however, the rate of fertility preservation and obstetrical outcome seem superior after neoadjuvant chemotherapy. Advantages and disadvantages of both options are discussed and a thorough literature review is provided. Issues to be further studied are also outlined.

  18. Intercalation of organic molecules in 2D copper (II) nitroprusside: Intermolecular interactions and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Osiry, H.; Cano, A.; Lemus-Santana, A.A.; Rodríguez, A. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional (Mexico); Carbonio, R.E. [INFIQC-CONICET, Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, X5000HUA Córdoba (Argentina); Reguera, E., E-mail: edilso.reguera@gmail.com [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional (Mexico)

    2015-10-15

    This contribution discusses the intercalation of imidazole and its 2-ethyl derivative, and pyridine in 2D copper nitroprusside. In the interlayer region, neighboring molecules remain interacting throu gh their dipole and quadrupole moments, which supports the solid 3D crystal structure. The crystal structure of this series of intercalation compounds was solved and refined from powder X-ray diffraction patterns complemented with spectroscopic information. The intermolecular interactions were studied from the refined crystal structures and low temperature magnetic measurements. Due to strong attractive forces between neighboring molecules, the resulting π–π cloud overlapping enables the ferromagnetic coupling between metal centers on neighboring layers, which was actually observed for the solids containing imidazole and pyridine as intercalated molecules. For these two solids, the magnetic data were properly described with a model of six neighbors. For the solid containing 2-ethylimidazole and for 2D copper nitroprusside, a model of four neighbors in a plane is sufficient to obtain a reliable data fitting. - Highlights: • Intercalation of organic molecules in 2D copper (II) nitroprusside. • Molecular properties of intercalation compounds of 2D copper (II) nitroprusside. • Magnetic properties of hybrid inorganic–organic solids. • Hybrid inorganic–organic 3D framework.

  19. Thermal analysis and infrared emission spectroscopic study of halloysite-potassium acetate intercalation compound

    International Nuclear Information System (INIS)

    The thermal decomposition of halloysite-potassium acetate intercalation compound was investigated by thermogravimetric analysis and infrared emission spectroscopy. The X-ray diffraction patterns indicated that intercalation of potassium acetate into halloysite caused an increase of the basal spacing from 1.00 to 1.41 nm. The thermogravimetry results show that the mass losses of intercalation the compound occur in main three main steps, which correspond to (a) the loss of adsorbed water, (b) the loss of coordination water and (c) the loss of potassium acetate and dehydroxylation. The temperature of dehydroxylation and dehydration of halloysite is decreased about 100 oC. The infrared emission spectra clearly show the decomposition and dehydroxylation of the halloysite intercalation compound when the temperature is raised. The dehydration of the intercalation compound is followed by the loss of intensity of the stretching vibration bands at region 3600-3200 cm-1. Dehydroxylation is followed by the decrease in intensity in the bands between 3695 and 3620 cm-1. Dehydration was completed by 300 oC and partial dehydroxylation by 350 oC. The inner hydroxyl group remained until around 500 oC.

  20. INTERPRETATION OF POTENTIAL INTERMITTENCE TITRATION TECHNIQUE EXPERIMENTS FOR VARIOUS Li-INTERCALATION ELECTRODES

    Directory of Open Access Journals (Sweden)

    M.D.Levi

    2002-01-01

    Full Text Available In this paper we compare two different approaches for the calculation of the enhancement factor Wi, based on its definition as the ratio of the chemical and the component diffusion coefficients for species in mixed-conduction electrodes, originated from the "dilute solution" or "lattice gas" models for the ion system. The former approach is only applicable for small changes of the ion concentration while the latter allows one to consider a broad range of intercalation levels. The component diffusion coefficient of lithium ions has been determined for a series of lithium intercalation anodes and cathodes. A new "enhancement factor" for the ion transport has been defined and its relations to the intercalation capacitance and the intercalation isotherm have been established. A correlation between the dependences of the differential capacitance and the partial ion conductivity on the potential has been observed. It is considered as a prove that the intercalation process is controlled by the availability of sites for Li-ion insertion rather than by the concurrent insertion of the counter-balancing electronic species.

  1. Synthesis of carbon black/carbon nitride intercalation compound composite for efficient hydrogen production.

    Science.gov (United States)

    Wu, Zhaochun; Gao, Honglin; Yan, Shicheng; Zou, Zhigang

    2014-08-21

    The photoactivity of g-C3N4 is greatly limited by its high recombination rate of photogenerated carriers. Coupling g-C3N4 with other materials has been demonstrated to be an effective way to facilitate the separation and transport of charge carriers. Herein we report a composite of conductive carbon black and carbon nitride intercalation compound synthesized through facile one-step molten salt method. The as-prepared carbon black/carbon nitride intercalation compound composite was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), UV-vis absorption spectrum and photoluminescence spectroscopy (PL). The carbon black nanoparticles, homogeneously dispersed on the surface of carbon nitride intercalation compound, efficiently enhanced separation and transport of photogenerated carriers, thus improving the visible-light photocatalytic activity. The composite of 0.5 wt% carbon black and carbon nitride intercalation compound exhibited a H2 production rate of 68.9 μmol h(-1), which is about 3.2 times higher than hydrogen production on pristine carbon nitride intercalation compound.

  2. Intercalation of urea into kaolinite for preparation of controlled release fertilizer

    Directory of Open Access Journals (Sweden)

    Mahdavi Fariba

    2014-01-01

    Full Text Available In this study urea was intercalated between layers of kaolinite by dry grinding technique to be used for preparing controlled release fertilizer. X-ray powder diffraction (XRPD patterns confirmed the intercalation of urea into kaolinite by the significant expansion of the basal spacing of kaolinite layers from 0.710 nm to 1.090 nm. Fourier transform infrared spectroscopy (FT-IR also confirmed the hydrogen bonding between urea and kaolinite. Based on CHNS elemental analysis, 20% (wt. urea was intercalated between kaolinite layers. The urea-intercalated kaolinite was mixed with hydroxypropyl methylcellulose (HPMC binder and was granulated to prepare the nitrogen-based controlled release fertilizer. To study the nitrogen release behavior of granules, ultraviolet/visible (UV-Vis spectroscopy was used through the diacetyl monoxime (DAM colorimetric method. The result of UV-Vis spectroscopy showed that intercalation of urea into kaolinite decreased the nitrogen release from 25.50 to 13.66 % after 24 hours and from 98.15 to 70.01% after 30 days incubation in water. According to the results, the prepared controlled release fertilizer (CRF behaved according to the standard for CRFs.

  3. Micromechanical properties of intercalated compounds of graphite oxide with dodecahydro- closо-dodecaboric acid

    Science.gov (United States)

    Karpenko, A. A.; Saldin, V. I.

    2016-08-01

    The micromechanical properties (Young's modulus, deformation, and adhesion) of the intercalated compound of graphite oxide with dodecahydro- closo-dodecaboric acid were studied by atomic force microscopy, transmission electron microscopy, and Raman spectroscopy and compared with the same characteristics of the starting graphite oxide. The significant difference in the micromechanical properties of the materials under study is dictated by differences in the topography and properties of their film surface, which, in turn, can be determined by their chemical composition. The introduction of dodecahydro- closo-dodecaboric acid in the interplanar space of graphite oxide affects the structuring of the latter. A considerable increase in the adhesion of the intercalated compound relative to that of oxide graphite is explained by high adhesive properties of the introduced acid, the Young's modulus of graphite oxide being higher than that of the intercalated compound. This was attributed to the high hydrophilicity of dodecahydro- closo-dodecaboric acid and the difficulty of water removal from the interplanar space; water plasticizes the material, which becomes softer than graphite oxide. The difference in the structure of the coating of the intercalated compounds and the starting graphite oxide was found to be also reflected by their Raman spectra, namely, by the increased intensity of the D line with the preserved position of the G line, which points to the impurity nature of the intercalate and the unchanged hexagonal lattice of graphite.

  4. Kaolinite Nanocomposite Platelets Synthesized by Intercalation and Imidization of Poly(styrene-co-maleic anhydride

    Directory of Open Access Journals (Sweden)

    Pieter Samyn

    2015-07-01

    Full Text Available A synthesis route is presented for the subsequent intercalation, exfoliation and surface modification of kaolinite (Kln by an imidization reaction of high-molecular weight poly(styrene-co-maleic anhydride or SMA in the presence of ammonium hydroxide. In a first step, the intercalation of ammonolyzed SMA by guest displacement of intercalated dimethylsulfoxide has been proven. In a second step, the imidization of ammonolyzed SMA at 160 °C results in exfoliation of the kaolinite layers and deposition of poly(styrene-co-maleimide or SMI nanoparticles onto the kaolinite surfaces. Compared with a physical mixture of Kln/SMI, the chemically reacted Kln/SMI provides more efficient exfoliation and hydrogen bonding between the nanoparticles and the kaolinite. The kaolinite nanocomposite particles are synthesized in aqueous dispersion with solid content of 65 wt %. The intercalation and exfoliation are optimized for a concentration ratio of Kln/SMI = 70:30, resulting in maximum intercalation and interlayer distance in combination with highest imide content. After thermal curing at 135 °C, the imidization proceeds towards a maximum conversion of the intermediate amic acid moieties. The changes in O–H stretching and kaolinite lattice vibrations have been illustrated by infrared and FT-Raman spectroscopy, which allow for a good quantification of concentration and imidization effects.

  5. Kinetics and thermodynamics of small molecule binding to pincer-PCP rhodium(I) complexes

    KAUST Repository

    Doherty, Mark D.

    2013-04-15

    The kinetics and thermodynamics of the binding of several small molecules, L (L = N2, H2, D2, and C2H 4), to the coordinatively unsaturated pincer-PCP rhodium(I) complexes Rh[tBu2PCH2(C6H3)CH 2PtBu2] (1) and Rh[tBu 2P(CH2)2(CH)(CH2)2P tBu2] (2) in organic solvents (n-heptane, toluene, THF, and cyclohexane-d12) have been investigated by a combination of kinetic flash photolysis methods, NMR equilibrium studies, and density functional theory (DFT) calculations. Using various gas mixtures and monitoring by NMR until equilibrium was established, the relative free energies of binding of N2, H2, and C2H4 in cyclohexane-d12 were found to increase in the order C 2H4 < N2 < H2. Time-resolved infrared (TRIR) and UV-vis transient absorption spectroscopy revealed that 355 nm excitation of 1-L and 2-L results in the photoejection of ligand L. The subsequent mechanism of binding of L to 1 and 2 to regenerate 1-L and 2-L is determined by the structure of the PCP ligand framework and the nature of the solvent. In both cases, the primary transient is a long-lived, unsolvated species (τ = 50-800 ns, depending on L and its concentration in solution). For 2, this so-called less-reactive form (LRF) is in equilibrium with a more-reactive form (MRF), which reacts with L at diffusion-controlled rates to regenerate 2-L. These two intermediates are proposed to be different conformers of the three-coordinate (PCP)Rh fragment. For 1, a similar mechanism is proposed to occur, but the LRF to MRF step is irreversible. In addition, a parallel reaction pathway was observed that involves the direct reaction of the LRF of 1 with L, with second-order rate constants that vary by almost 3 orders of magnitude, depending on the nature of L (in n-heptane, k = 6.7 × 10 5 M-1 s-1 for L = C2H4; 4.0 × 106 M-1 s-1 for L = N2; 5.5 × 108 M-1 s-1 for L = H2). Experiments in the more coordinating solvent, THF, revealed the binding of THF to 1 to generate 1-THF, and its subsequent reaction with L, as a

  6. Consolidation Radiotherapy in Stage IE- IIE, Non-Bulky Primary Gastric Diffuse Large B-Cell Lymphoma with Post-Chemotherapy Complete Remission.

    Directory of Open Access Journals (Sweden)

    Qiwen Li

    Full Text Available To investigate the effects of consolidation radiation in patients with stage IE-IIE, non-bulky primary gastric diffuse large B-cell lymphoma (DLBCL.A cohort consisted of 71 consecutive patients with stage IE-IIE, non-bulky primary gastric DLBCL was retrospectively analyzed. All of them had been in complete remission after receiving at least four cycles of chemotherapy, containing rituximab or not. Consolidation radiation was delivered thereafter in 28 patients while other 43 received clinical observation only. Locoregional relapse-free survival (LRFS, disease-free survival (DFS, overall survival (OS and distant metastasis-free survival (DMFS were compared between patients with or without radiotherapy.The 10-year LRFS, DFS, OS and DMFS were 100% and 81.4% (p = 0.028, 91.7% and 77.1% (p = 0.14, 91.7% and 77.8% (p = 0.67, 91.7% and 78.0% (p = 0.42 for patients with or without radiotherapy.Radiotherapy is associated with improved locoregional control of patients with early stage primary gastric DLBCL, who have achieved complete remission following at least four cycles of chemotherapy.

  7. Extremely bulky amido first row transition metal(II) halide complexes: potential precursors to low coordinate metal-metal bonded systems.

    Science.gov (United States)

    Hicks, Jamie; Jones, Cameron

    2013-04-01

    Reactions of the extremely bulky potassium amide complexes, [KL'(η(6)-toluene)] or [KL"] (L'/L" = N(Ar*)(SiR3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4; R = Me (L') or Ph (L")), with a series of first row transition metal(II) halides have yielded 10 rare examples of monodentate amido first row transition metal(II) halide complexes, all of which were crystallographically characterized. They encompass the dimeric, square-planar chromium complexes, [{CrL'(THF)(μ-Cl)}2] and [{CrL"(μ-Cl)}2], the latter of which displays intramolecular η(2)-Ph···Cr interactions; the dimeric tetrahedral complexes, [{ML'(THF)(μ-Br)}2] (M = Mn or Fe), [{ML"(THF)(μ-X)}2] (M = Mn, Fe or Co; X = Cl or Br) and [{CoL"(μ-Cl)}2] (which displays intramolecular η(2)-Ph···Co interactions); and the monomeric zinc amides, [L'ZnBr(THF)] (three-coordinate) and [L"ZnBr] (two-coordinate). Solution state magnetic moment determinations on all but one of the paramagnetic compounds show them to be high-spin systems. Throughout, comparisons are made with related bulky terphenyl transition metal(II) halide complexes, and the potential for the use of the prepared complexes as precursors to low-valent transition metal systems is discussed.

  8. Radiosensitization by the novel DNA intercalating agent vosaroxin

    Directory of Open Access Journals (Sweden)

    Gordon Ira K

    2012-02-01

    Full Text Available Abstract Purpose Vosaroxin is a first in class naphthyridine analog structurally related to quinolone antibacterials, that intercalates DNA and inhibits topoisomerase II. Vosaroxin is not a P-glycoprotein receptor substrate and its activity is independent of p53, thus evading common drug resistance mechanisms. To evaluate vosaroxin as a clinically applicable radiation sensitizer, we investigated its effects on tumor cell radiosensitivity in vitro and in vivo. Methods Vosaroxin's effect on post-irradiation sensitivity of U251, DU145, and MiaPaca-2 cells was assessed by clonogenic assay. Subsequent mechanistic and in vivo studies were performed with U251 cells. Cell cycle distribution and G2 checkpoint integrity was analyzed by flow cytometry. DNA damage and repair was evaluated by a high throughput gamma-H2AX assay. Apoptosis was assessed by flow cytometry. Mitotic catastrophe was assessed by microscopic evidence of fragmented nuclei by immunofluorescence. In vivo radiosensitization was measured by subcutaneous tumor growth delay. Results 50-100 nmol/L treatment with vosaroxin resulted in radiosensitization of all 3 cell lines tested with a dose enhancement factor of 1.20 to 1.51 measured at a surviving fraction of 0.1. The maximal dose enhancement was seen in U251 cells treated with 75 nmol/L vosaroxin (DEF 1.51. Vosaroxin exposure did not change cell cycle distribution prior to irradiation nor alter G2 checkpoint integrity after irradiation. No difference was seen in the apoptotic fraction regardless of drug or radiation treatment. The number of cells in mitotic catastrophe was significantly greater in irradiated cells treated with vosaroxin than cells receiving radiation only at 72 hr (p = 0.009. Vosaroxin alone did not significantly increase mitotic catastrophe over control (p = 0.53. Cells treated with vosaroxin and radiation maintained significantly higher gamma-H2AX levels than cells treated with vehicle control (p = 0.014, vosaroxin (p

  9. SYNTHESIS OF POLY(VINYL ACETATE)-INTERCALATED GRAPHITE OXIDE BY AN IN SITU INTERCALATIVE POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Ping-gui Liu; Peng Xiao; Min Xiao; Ke-cheng Gong

    2000-01-01

    Graphite oxide, a pseudo-two-dimensional solid in bulk form, was synthesized from natural graphite powder by oxidization with KMnO4 in concentrated H2SO4. The poly(vinyl acetate)-intercalated graphite oxide nano-composite was prepared by an in situ intercalative polymerization reaction, in which n-octanol-graphite oxide intercalation compounds were first obtained, vinyl acetate monomer was then dispersed into the interlayer of modified graphite oxide, followed by thermal polymerization of the monomer. It was experimentally shown that the c-axis space ofpoly(vinyl acetate)-intercalated graphite oxide was increased to 0.115 nm, which suggested there existed a monolayer of poly(vinyl acetate) chain between the layers of graphite oxide. The nanocomposite was also characterized with thermal analysis and FT-IR spectrometry.

  10. Keeping argon under a graphene lid-Argon intercalation between graphene and nickel(111)

    Science.gov (United States)

    Späth, Florian; Gotterbarm, Karin; Amende, Max; Bauer, Udo; Gleichweit, Christoph; Höfert, Oliver; Steinrück, Hans-Peter; Papp, Christian

    2016-01-01

    We report on the intercalation of graphene grown on a Ni(111) crystal with argon. Argon is implanted in the Ni(111) crystal by ion bombardment before graphene growth, and diffuses to the surface during the growth of graphene at elevated temperatures. Graphene acts as an atomically thin barrier and keeps the argon underneath. We investigated this system with high resolution X-ray photoelectron spectroscopy. From our experiments we determined the mean quantities of argon under graphene. From our analysis, a simple model to determine the pressure under the graphene layer is presented. In our measurements, we find an increased thermal stability of the intercalated graphene as compared to non-intercalated graphene on Ni(111).

  11. Structure model and synthesis of NdCl3-FeCl3-graphite intercalation compounds

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The distribution of the elements and microstructure of NdCl3-FeCl3-graphite intercalation compounds (GICs) were shown by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS). The results show that Nd element intercalates into graphite, forming NdCl3-FeCl3-GICs, and the distribution of Nd and Fe is nearly even. On the basis of the data, a structure model for RECl3-GICs was founded, and the characteristic layer distance and the index of interval energy were calculated. The calculated results agree with experimental ones, and the relative errors are ±2%. Thus it can be seen that the (111) face is optimal direction for intercalation reaction of TbCl3 LuCl3, and the (001) face is that for LaCl3 GdCl3, because of the lowest interval energy.

  12. Structure model and synthesis of NdCl3-FeCl3-graphite intercalation compounds

    Institute of Scientific and Technical Information of China (English)

    侯仰龙[1; 韦永德[2; 石建新[3

    2000-01-01

    The distribution of the elements and microstructure of NdCI3-FeCI3-graphite intercalation compounds (GICs) were shown by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS). The results show that Nd element intercalates into graphite, forming NdCI3-FeCI3-GICs, and the distribution of Nd and Fe is nearly even. On the basis of the data, a structure model for RECI3-GICs was founded, and the characteristic layer distance and the index of interval energy were calculated. The calculated results agree with experimental ones, and the relative errors are ±2%. Thus it can be seen that the (111) face is optimal direction for intercalation reaction of TbCl3-LuCl3, and the (001) face is that for LaCl3-GdCl3, because of the lowest interval energy.

  13. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide.

    Science.gov (United States)

    Lukatskaya, Maria R; Mashtalir, Olha; Ren, Chang E; Dall'Agnese, Yohan; Rozier, Patrick; Taberna, Pierre Louis; Naguib, Michael; Simon, Patrice; Barsoum, Michel W; Gogotsi, Yury

    2013-09-27

    The intercalation of ions into layered compounds has long been exploited in energy storage devices such as batteries and electrochemical capacitors. However, few host materials are known for ions much larger than lithium. We demonstrate the spontaneous intercalation of cations from aqueous salt solutions between two-dimensional (2D) Ti3C2 MXene layers. MXenes combine 2D conductive carbide layers with a hydrophilic, primarily hydroxyl-terminated surface. A variety of cations, including Na(+), K(+), NH4(+), Mg(2+), and Al(3+), can also be intercalated electrochemically, offering capacitance in excess of 300 farads per cubic centimeter (much higher than that of porous carbons). This study provides a basis for exploring a large family of 2D carbides and carbonitrides in electrochemical energy storage applications using single- and multivalent ions.

  14. Hydroxy double salts intercalated with Mn(II) complexes as potential contrast agents

    Science.gov (United States)

    Jin, Miao; Li, Wanjing; Spillane, Dominic E. M.; Geraldes, Carlos F. G. C.; Williams, Gareth R.; Bligh, S. W. Annie

    2016-03-01

    A series of Mn(II) aminophosphonate complexes were successfully synthesized and intercalated into the hydroxy double salt [Zn5(OH)8]Cl2·yH2O. Complex incorporation led to an increase in the interlayer spacing from 7.8 to 10-12 Å. Infrared spectroscopy showed the presence of the characteristic vibration peaks of the Mn(II) complexes in the intercalates' spectra, indicating successful incorporation. The complex-loaded composites had somewhat lower proton relaxivities than the pure complexes. Nevertheless, these intercalates may have use as MRI contrast agents for patients with poor kidney function, where traditional Gd(III)-based contrast agents cause severe renal failure.

  15. Preparation of the Thermoplastic Starch/Montmorillonite Nanocomposites by Melt-intercalation

    Institute of Scientific and Technical Information of China (English)

    Ming Fu HUANG; Jiu Gao YU; Xiao Fei MA

    2005-01-01

    In this paper, the conception of melt-intercalation was introduced into the natural polymer field, and the thermoplastic starch/ethanolamine-activated montmorillonite (TPS/EMMT)nanocomposites were prepared by extruding the composites of EMMT and TPS, plasticized with ethanolamine/formamide. Wide angle X-ray diffraction (WAXD) and transmission electron microscope (TEM) revealed that TPS was intercalated into the layers of EMMT successfully and formed the intercalation nanocomposites with EMMT. When EMMT content was wt. 10%, the mechanical testing indicated that the tensile stress of the nanocomposites reached 9.69 MPa, and the tensile strain reached 74.07%, Youngs modulus increased from the 47.23 MPa of TPS to 184.11after they had been stored at RH25% for 14 days.

  16. Structural Analysis of Layered Polymer Crystals and Application to Photofunctional Materials Using Organic Intercalation

    Institute of Scientific and Technical Information of China (English)

    Shinya Oshita; Akikazu Matsumoto

    2005-01-01

    @@ 1Introduction We reported that layered polymer crystals are obtained by the topochemical polymerization of 1,3-diene monomers and provided as host material for organic intercalation[1]. For intercalation using various long-alkyl amines as the guest species, its reaction behavior, mechanism, characteristics, and potential to application have been clarified[2]. We also succeeded in the synthesis of several host layered polymer crystals with different tacticities and layer structures[3]. We describe here intercalation using various stereoregular poly(muconic acid)s (PMA) and n-alkylamines as the host and guest compounds, respectively. The reaction behavior and the layered structure of the obtained ammonium polymers are discussed from the viewpoint of stereochemical structure of the host polymers.

  17. Preparation of poly(propylene carbonate)/organophilic rectorite nanocomposites via direct melt intercalation

    Institute of Scientific and Technical Information of China (English)

    WAN Chun-jie; YU Jian-ying; SHI Xiao-jian; HUANG Li-hua

    2006-01-01

    The completely degradable nanocomposites comprised of poly(propylene carbonate)(PPC) and organo-modified rectorite (OREC) were prepared by direct melt intercalation. The structure and mechanical properties of PPC/OREC nanocomposites were investigated. The wide-angle X-ray diffraction (WAXD) results show that the galleries distance of OREC is increased after PPC and OREC melt intercalation,which indicates that PPC molecular chain has intercalated into the layers of OREC. The PPC/OREC nanocomposites with lower OREC content show an increase in thermal decomposition temperature compared with pure PPC. The tensile strength and impact strength of PPC/OREC nanocomposites are improved. When the mass fraction of OREC is 4%,the tensile strength and impact strength of the PPC/OREC nanocomposite increase by 22.86% and 48.58% respectively,compared with pure PPC.

  18. Electron doping through lithium intercalation to interstitial channels in tetrahedrally bonded SiC

    Energy Technology Data Exchange (ETDEWEB)

    Sakai, Yuki [Department of Applied Physics, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Center for Computational Materials, Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, Texas 78712 (United States); Oshiyama, Atsushi [Department of Applied Physics, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)

    2015-11-07

    We report on first-principles calculations that clarify the effect of lithium atom intercalation into zinc blende 3C-silicon carbide (3C-SiC) on electronic and structural properties. Lithium atoms inside 3C-SiC are found to donate electrons to 3C-SiC that is an indication of a new way of electron doping through the intercalation. The electrons doped into the conduction band interact with lithium cations and reduce the band spacing between the original valence and conduction bands. We have also found that a silicon monovacancy in 3C-SiC promotes the lithium intercalation, showing that the vacancy generation makes SiC as a possible anode material for lithium-ion battery.

  19. Thermoelectric Properties of Li-Intercalated ZrSe2 Single Crystals

    DEFF Research Database (Denmark)

    Holgate, Tim; Liu, Yufei; Hitchcock, Dale;

    2013-01-01

    can profoundly affect the structural, thermal, and electronic properties of such materials. While the thermoelectric potential of layer-structured transitionmetal dichalcogenides has been formerly studied by several groups, to our best knowledge, neither the thermoelectric properties of ZrSe2 nor...... the impact of intercalation on its thermoelectric properties have been reported (specifically, the full evaluation of the dimensionless figure of merit, ZT, which includes the thermal conductivity). In this proof-of-principle study, ZrSe2 single crystals have been synthesized using an iodine-assisted vapor...... transport method, followed by a wet-chemistry lithium intercalation process. The results of resistivity, thermopower, and thermal conductivity measurements between 10 K and 300 K show that Li intercalation induced additional charge carriers and structural disorder that favorably affected the thermoelectric...

  20. Synthesis and Characterization of Ibuprofen-Rectorite Composites by Solution Intercalation Method

    Institute of Scientific and Technical Information of China (English)

    WANG Huiyan; ZHANG Gaoke; GAN Huihu; GAO Yuanyuan

    2009-01-01

    The ibuprofen-rectorite composites were prepared by the solution intercalation method using ibuprofen and rectorite as raw materials,and were characterized by X-ray diffraction (XRD)analysis,Fourier transform infrared analysis and scanning electron microscopy(SEM).The experimental results show that the ibuprofen is intercalated into the interlayer spaces of rectorite.The values of the(001)peaks of the ibuprofen-rectorite composite are larger than that of Na-rectorite and reach the largest when the reaction time and ibuprofen amount is 2 h and 0.36 g,respectively.The layered structure of Na-rectorite is destroyed to some extent with the intercalation of ibuprofen into the interlayer space in the structure of Na-rectorite.A part of ibuprofen in the ibuprofen Na-rectorite covers on the surface of Na-rectorite besides some ibuprofen enters into the interlayer space.

  1. Hydroxy double salts loaded with bioactive ions: Synthesis, intercalation mechanisms, and functional performance

    Science.gov (United States)

    Y. A. Kaassis, Abdessamad; Xu, Si-Min; Guan, Shanyue; Evans, David G.; Wei, Min; Williams, Gareth R.

    2016-06-01

    The intercalation of the anions of diclofenac (Dic), naproxen (Nap), and valproic acid (Val) into three hydroxy double salts (HDSs) has been explored in this work. Experiments were performed with [Co1.2Zn3.8(OH)8](NO3)2·2H2O (CoZn-NO3), [Ni2Zn3(OH)8](NO3)2·2H2O (NiZn-NO3) and [Zn5(OH)8](NO3)2·2H2O (Zn-NO3). It proved possible to intercalate diclofenac and naproxen into all three HDSs. In contrast, Val could be intercalated into CoZn-NO3 but when it was reacted with Zn-NO3 the HDS structure was destroyed, and the product comprised ZnO. Successful intercalation was verified by X-ray diffraction, IR spectroscopy, and elemental microanalysis. Molecular dynamics simulations showed the Dic and Nap ions to arrange themselves in an "X" shape in the interlayer space, forming a bilayer. Val was found to adopt a position with its aliphatic groups parallel to the HDS layer, again in a bilayer. In situ time resolved X-ray diffraction experiments revealed that intercalation of Dic and Nap into CoZn-NO3 and Zn-NO3 is mechanistically complex, with a number of intermediate phases observed. In contrast, the intercalation of all three guests into NiZn-NO3 and of Val into CoZn-NO3 are simple one step reactions proceeding directly from the starting material to the product. The HDS-drug composites were found to have sustained release profiles.

  2. Adsorption and intercalation of anionic surfactants onto layered double hydroxides—XRD study

    Indian Academy of Sciences (India)

    R Anbarasan; W D Lee; S S Im

    2005-04-01

    Layered double hydroxides (LDH) with brucite like structure was modified with various anionic surfactants containing sulfonate, carboxyl, phosphonate and sulfate end group through ion-exchange method. XRD reports indicated that the sulfonate group containing surfactants led to an adsorption process whereas the sulfate, carboxyl and phosphonate group containing surfactant led to an intercalation process. This can be evidenced from the change in basal spacing of LDH. The presence of anionic surfactants in the LDH was supported by FTIR spectroscopy. The FTIR spectrum indicated that complete removal of carbonate anion from the inter layer space of LDH is very difficult. The phosphonate intercalated HT showed less thermal stability than pristine LDH.

  3. Probing the recognition surface of a DNA triplex: binding studies with intercalator-neomycin conjugates.

    Science.gov (United States)

    Xue, Liang; Xi, Hongjuan; Kumar, Sunil; Gray, David; Davis, Erik; Hamilton, Paris; Skriba, Michael; Arya, Dev P

    2010-07-01

    Thermodynamic studies on the interactions between intercalator-neomycin conjugates and a DNA polynucleotide triplex [poly(dA).2poly(dT)] were conducted. To draw a complete picture of such interactions, naphthalene diimide-neomycin (3) and anthraquinone-neomycin (4) conjugates were synthesized and used together with two other analogues, previously synthesized pyrene-neomycin (1) and BQQ-neomycin (2) conjugates, in our investigations. A combination of experiments, including UV denaturation, circular dichroism (CD) titration, differential scanning calorimetry (DSC), and isothermal titration calorimetry (ITC), revealed that all four conjugates (1-4) stabilized poly(dA).2poly(dT) much more than its parent compound, neomycin. UV melting experiments clearly showed that the temperature (T(m3-->2)) at which poly(dA).2poly(dT) dissociated into poly(dA).poly(dT) and poly(dT) increased dramatically (>12 degrees C) in the presence of intercalator-neomycin conjugates (1-4) even at a very low concentration (2 muM). In contrast to intercalator-neomycin conjugates, the increment of T(m3-->2) of poly(dA).2poly(dT) induced by neomycin was negligible under the same conditions. The binding preference of intercalator-neomycin conjugates (1-4) to poly(dA).2poly(dT) was also confirmed by competition dialysis and a fluorescent intercalator displacement assay. Circular dichroism titration studies revealed that compounds 1-4 had slightly larger binding site size ( approximately 7-7.5) with poly(dA).2poly(dT) as compared to neomycin ( approximately 6.5). The thermodynamic parameters of these intercalator-neomycin conjugates with poly(dA).2poly(dT) were derived from an integrated van't Hoff equation using the T(m3-->2) values, the binding site size numbers, and other parameters obtained from DSC and ITC. The binding affinity of all tested ligands with poly(dA).2poly(dT) increased in the following order: neomycin neomycin. The binding of compounds 1-4 with poly(dA).2poly(dT) was mostly enthalpy

  4. Synthesis, characterization and properties of polyaniline/expanded vermiculite intercalated nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Lin Jianming; Tang Qunwei; Wu Jihuai; Sun Hui [Key Laboratory of Functional Materials for Fujian Higher Education, Institute of Material Physical Chemistry, Huaqiao University, Quanzhou 362021 (China)], E-mail: jhwu@hqu.edu.cn

    2008-04-15

    The synthesis characterization and conductivities of polyaniline/expanded vermiculite intercalated nanocomposite are presented in this paper. The conductive emeraldine salt form of polyaniline is inserted into the interlayer of expanded vermiculite to produce the nanocomposite with high conductivity. The structures and properties are characterized by transmission electron microscopy x-ray diffraction spectroscopy fourier transform infrared spectroscopy thermogravimetry analysis and by the measurements of conductivity and stability. The results show that an intercalated nanocomposite with high conductivity and stability is obtained. The synthesis conditions are optimized to obtain the highest conductivity which is 6.80 S cm{sup -1}.

  5. Synthesis, characterization and properties of polyaniline/expanded vermiculite intercalated nanocomposite

    Directory of Open Access Journals (Sweden)

    Jianming Lin, Qunwei Tang, Jihuai Wu and Hui Sun

    2008-01-01

    Full Text Available The synthesis characterization and conductivities of polyaniline/expanded vermiculite intercalated nanocomposite are presented in this paper. The conductive emeraldine salt form of polyaniline is inserted into the interlayer of expanded vermiculite to produce the nanocomposite with high conductivity. The structures and properties are characterized by transmission electron microscopy x-ray diffraction spectroscopy fourier transform infrared spectroscopy thermogravimetry analysis and by the measurements of conductivity and stability. The results show that an intercalated nanocomposite with high conductivity and stability is obtained. The synthesis conditions are optimized to obtain the highest conductivity which is 6.80 S cm−1.

  6. Mg2Si As Li-Intercalation Host For Li Cells

    Science.gov (United States)

    Huang, Chen-Kuo; Surampudi, Subbarao; Attia, Alan; Halpert, Gerald

    1993-01-01

    Compound Mg2Si shows promise as lithium-intercalation host for ambient-temperature rechargeable lithium electrochemical cells. As anode reactant material, LiXMg2Si chemically stable in presence of organic electrolyte used in such cells and stores large amounts of lithium. Intercalation reactions highly reversible at room temperature. Also retains sufficient mechanical strength during charge/discharge cycling. Lithium cells containing LixMg2Si anodes prove useful in spacecraft, military, communications, automotive, and other applications in which high energy-storage densities of lithium cells in general and rechargeability of cells needed.

  7. NBR/ORGANOMODIFIED BENTONITE INTERCALATED HYBRIDS AND THEIR EFFECTS ON THE TOUGHNESS OF PVC

    Institute of Scientific and Technical Information of China (English)

    Chang-jiang You; De-min Jia; Zeng-yong Zhen; Kui Ding; Song Xi; Hai-lin Mo; Yong-hua Zhang

    2003-01-01

    Hybrids of intercalative nitrile-butadiene rubber/organomodified bentonite (NBR/OMB) were prepared by the latex intercalation technique. Investigation of their mechanical properties and the microstructure of NBR/OMB showed that the organomodified bentonite is an effective toughener for NBR. Transmission electronic microscopy (TEM) and X-ray diffraction (XRD) tests showed that the NBR macromolecule could be intercalated into the galleries of bentonite.Incorporation of NBR/OMB hybrids as tougheners into poly(vinyl chloride) (PVC) results in a substantial increase in the impact strength of PVC, but little decrease in its tensile strength and flexural strength, compared to the unmodified PVC.

  8. THE NANOCOMPOSITE FILM OF POLYMER INTERCALATION IN V2O5 XEROGEL

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The nanocomposite films were prepared by poly(ethylene oxide), PEO, intercalation in V2O5 xerogel in sol-gel. The synthesis and state of the films are investigated by the XRD, IR, SEM, etc. The results show that V2O5 xerogel is a layered structure which arranges in c-direction. The interlayer distance of V2O5 xerogel increases remarkably when PEO is intercalated in V2O5 xerogel interlayer. PEO has strong interaction with V2O5 host. The surface of the films is homogeneous without holes and cracks.

  9. The effect of hydrazine intercalation on the structure and capacitance of 2D titanium carbide (MXene).

    Science.gov (United States)

    Mashtalir, O; Lukatskaya, M R; Kolesnikov, A I; Raymundo-Piñero, E; Naguib, M; Barsoum, M W; Gogotsi, Y

    2016-04-28

    Herein we show that hydrazine intercalation into 2D titanium carbide (Ti3C2-based MXene) results in changes in its surface chemistry by decreasing the amounts of fluorine, OH surface groups and intercalated water. It also creates a pillaring effect between Ti3C2Tx layers pre-opening the structure and improving the accessability to active sites. The hydrazine treated material has demonstrated a greatly improved capacitance of 250 F g(-1) in acidic electrolytes with an excellent cycling ability for electrodes as thick as 75 μm.

  10. Ab initio investigation of the Jahn-Teller distortion effect on the stabilizing lithium intercalated compounds

    International Nuclear Information System (INIS)

    This paper reports on a fundamental study of the Jahn-Teller distortion effect after lithium intercalation in transition metal oxides, using the density functional theory in the local spin density approximation. The intercalation of lithium in cobalt oxide was found to form a stable compound with an α-NaFeO2 crystal structure. An unstable structure was found to form for the nickel oxide compound. An important Jahn-Teller distortion was observed in MnO2 and LiMnO2, and the structure was found to be unstable. These theoretical results are in agreement with the experimental findings in the literature

  11. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Songchen [Ames Laboratory; Manna, Kuntal [Ames Laboratory; Ellern, Arkady [Ames Laboratory; Sadow, Aaron D [Ames Laboratory

    2014-12-08

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis

  12. Electrodeposition of ruthenium, rhodium and palladium from nitric acid and ionic liquid media: Recovery and surface morphology of the deposits

    International Nuclear Information System (INIS)

    Research highlights: → Platinum group metals are man-made noble metals. → Electrochemical recovery of fission platinoids. → Recovery from nitric acid medium. → Recovery from ionic liquid medium. → Platinoids with exotic surface morphologies. - Abstract: Electrodeposition is a promising technique for the recovery of platinum group metals with unique surface morphologies. The electrodeposition of palladium, ruthenium and rhodium from aqueous nitric acid, and non-aqueous 1-butyl-3-methylimidazolium chloride ionic liquid medium was studied at stainless steel electrode. The surface morphology and elemental composition of the resultant deposit were probed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDS) analysis. Deposits with diverse surface morphologies and metal compositions were obtained by varying the composition of the electrolytic medium and applied potential. The results demonstrate the possibility of tailoring the morphologies of PGMs by controlling the composition and potential needed for electrodeposition.

  13. New Diphosphine Ligands Containing Ethyleneglycol and Amino Alcohol Spacers for the Rhodium-Catalyzed Carbonylation of Methanol

    OpenAIRE

    Thomas, Christophe M; Mafua, Roger; Therrien, Bruno; Rusanov, Eduard; Stoeckli-Evans, Helen; Süss-Fink, Georg

    2006-01-01

    The new diphosphine ligands Ph2PC6H4C(O)X(CH2)2OC(O)C6H4PPh2 (1: X=NH; 2: X=NPh; 3: X=O) and Ph2PC6H4C(O)O(CH2)2O(CH2)2OC(O)C6H4PPh2 (5) as well as the monophosphine ligand Ph2PC6H4C(O)X(CH2)2OH (4) have been prepared from 2-diphenylphosphinobenzoic acid and the corresponding amino alcohols or diols. Coordination of the diphosphine ligands to rhodium, iridium, and platinum resulted in the formation of the square-planar complexes [(PP)Rh(CO)Cl] (6: PP=1; 7: PP=2; 8: PP=3), [(PP)Rh(CO)Cl]2 (9: ...

  14. An advanced model for the prediction of the total burnup-dependent self-powered rhodium detector response

    International Nuclear Information System (INIS)

    This paper presents an advanced method to generate the burnup dependent total response of a rhodium self-powered detector operating in a pressurized water reactor environment. Full use is made of advanced nodal neutronic and coupled electron-photon transport techniques. The method accounts for (1) the detailed energy and spatial dependence of the neutron activation of each detector segment in a three-dimensional representation, (2) the generation of electrons caused by both neutron and gamma interactions in all the geometrical regions of the detector, and (3) the transport of the electrons within the detector to provide an observable current. All components of the detector signal are directly calculated - the method does not require the use of any empirical data, such as detector sensitivities. Intermediate results, such as beta escape fractions, were compared to measured data, and the overall technique was extensively benchmarked against operating data from three reactors

  15. A New Synthetic Method of Rhodium Iodide%三碘化铑的新合成方法

    Institute of Scientific and Technical Information of China (English)

    刘桂华; 匡飞平; 潘再富; 余尧; 侯文明; 沈善问; 高金翠; 杨军; 彭玉玲; 杨善晓

    2012-01-01

    A new method has been introduced to synthesize rhodium iodide, an important homogenous catalyst for earbonylation of methanol, to overcome shortcomings of the present methods. These shortcomings include low yield, poor quality and unacceptability with respect to industrial manufacturing. The new method involves the direct reaction of RhC13 with HI. The yield is up to 98.5% and Cl-ean be minimized to 50 ppm by optimizing synthetic operations, superior to the reported data.%三氯化铑与氢碘酸直接合成碘化铑,在最佳反应条件下,合成的收率达到98.5%,产品晶形均一,氯离子含量小于50 mg/kg。

  16. Site-specific intercalation at the triplex-duplex junction induces a conformational change which is detectable by hypersensitivity to diethylpyrocarbonate.

    OpenAIRE

    Collier, D A; Mergny, J L; Thuong, N T; Helene, C

    1991-01-01

    Using site-specific intercalation directed by intermolecular triplex formation, the conformation of an intercalation site in DNA was examined by footprinting with the purine-specific (A much greater than G) reagent diethylpyrocarbonate. Site specific intercalation was achieved by covalently linking an intercalator to the 5' end of a homopyrimidine oligodeoxynucleotide, which bound to a homopurinehomopyrimidine stretch in a recombinant plasmid via intermolecular triplex formation. This directs...

  17. Synthesis and application of Amberlite xad-4 functionalized with alizarin red-s for preconcentration and adsorption of rhodium (III

    Directory of Open Access Journals (Sweden)

    Sid Kalal Hossein

    2012-09-01

    Full Text Available Abstract A new chelating resin was prepared by coupling Amberlite XAD-4 with alizarin red-s through an azo spacer, characterized by infra-red spectroscopy and thermal analysis and studied for Rh(III preconcentration using inductively coupled plasma atomic emission spectroscopy (ICP-AES for rhodium monitoring in the environment. The optimum pH for sorption of the metal ion was 6.5. The sorption capacity was found 2.1 mg/g of resin for Rh(III. A recovery of 88% was obtained for the metal ion with 1.5 M HCl as eluting agent. Kinetic adsorption data were analyzed by adsorption and desorption times of Rh(III on modified resin. Scat chard analysis revealed that the homogeneous binding sites were formed in the polymers. The linear regression equation was Q/C = –1.3169Q + 27.222 (R2 = 0.9239, for Rh were formed in the SPE sorbent,Kd and Qmax for the affinity binding sites were calculated to be 0.76 μmol/mL and 20.67 μmol/g, respectively. The equilibrium data and parameters of Rh(III adsorption on modified resin were analyzed by Langmuir, Freundlich, Temkin and Redlich–Peterson models. The experimental adsorption isotherm was in good concordance with Langmuir and Freundlich models (R2 > 0.998 and based on the Langmuir isotherm the maximum amount of adsorption (qmax was 4.842 mg/g. The method was applied for rhodium ions determination in environmental samples. with high recovery (>80%.

  18. Synthesis and Application of Amberlite Xad-4 Functionalized with Alizarin Red-S for Preconcentration and Adsorption of Rhodium (iii

    Directory of Open Access Journals (Sweden)

    Hossein Sid Kalal

    2012-09-01

    Full Text Available A new chelating resin was prepared by coupling Amberlite XAD-4 with alizarin red-s through an azo spacer, characterized by infra-red spectroscopy and thermal analysis and studied for Rh(III preconcentration using inductively coupled plasma atomic emissionspectroscopy (ICP-AES for rhodium monitoring in the environment. The optimum pH for sorption of the metal ion was 6.5. The sorption capacity was found 2.1 mg/g of resin for Rh(III. A recovery of 88% was obtained for the metal ion with 1.5 M HCl as eluting agent.Kinetic adsorption data were analyzed by adsorption and desorption times of Rh(III on modified resin. Scat chard analysis revealed that the homogeneous binding sites were formed in the polymers. The linear regression equation was Q/C = –1.3169Q + 27.222 (R2 = 0.9239,for Rh were formed in the SPE sorbent,Kd and Qmax for the affinity binding sites were calculated to be 0.76 μmol/mL and 20.67 μmol/g, respectively. The equilibrium data and parameters of Rh(III adsorption on modified resin were analyzed by Langmuir, Freundlich,Temkin and Redlich–Peterson models. The experimental adsorption isotherm was in good concordance with Langmuir and Freundlich models (R2 > 0.998 and based on the Langmuir isotherm the maximum amount of adsorption (qmax was 4.842 mg/g. The method was applied for rhodium ions determination in environmental samples. with high recovery (>80%.

  19. Group 1 and group 2 metal complexes supported by a bidentate bulky iminopyrrolyl ligand: synthesis, structural diversity, and ε-caprolactone polymerization study.

    Science.gov (United States)

    Kottalanka, Ravi K; Harinath, A; Rej, Supriya; Panda, Tarun K

    2015-12-14

    We report here a series of alkali and alkaline earth metal complexes, each with a bulky iminopyrrolyl ligand [2-(Ph3CN=CH)C4H3NH] (1-H) moiety in their coordination sphere, synthesized using either alkane elimination or silylamine elimination methods or the salt metathesis route. The lithium salt of molecular composition [Li(2-(Ph3CN=CH)C4H3N)(THF)2] (2) was prepared using the alkane elimination method, and the silylamine elimination method was used to synthesize the dimeric sodium and tetra-nuclear potassium salts of composition [(2-(Ph3CN=CH)C4H3N)Na(THF)]2 (3) and [(2-(Ph3CN=CH)C4H3N)K(THF)0.5]4 (4) respectively. The magnesium complex of composition [(THF)2Mg(CH2Ph){2-(Ph3CN=CH)C4H3N}] (5) was synthesized through the alkane elimination method, in which [Mg(CH2Ph)2(OEt2)2] was treated with the bulky iminopyrrole ligand 1-H in 1 : 1 molar ratio, whereas the bis(iminopyrrolyl)magnesium complex [(THF)2Mg{2-(Ph3CN=CH)C4H3N}2] (6) was isolated using the salt metathesis route. The heavier alkaline earth metal complexes of the general formula {(THF)nM(2-(Ph3CN=CH)C4H3N)2} [M = Ca (7), Sr (8), and n = 2; M = Ba (9), n = 3] were prepared in pure form using two synthetic methods: in the first method, the bulky iminopyrrole ligand 1-H was directly treated with the alkaline earth metal precursor [M{N(SiMe3)2}2(THF)n] (where M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent at ambient temperature. The complexes 7-9 were also obtained using the salt metathesis reaction, which involves the treatment of the potassium salt (4) with the corresponding metal diiodides MI2 (M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent. The molecular structures of all the metal complexes (1-H, 2-9) in the solid state were established through single-crystal X-ray diffraction analysis. The complexes 5-9 were tested as catalysts for the ring-opening polymerization of ε-caprolactone. High activity was observed in the heavier alkaline earth metal complexes 7-9, with a very

  20. Clinical Analysis of stereotactic body radiation therapy using extracranial gamma knife for patients with mainly bulky inoperable early stage non-small cell lung carcinoma

    Directory of Open Access Journals (Sweden)

    Tang Hanjun

    2011-07-01

    Full Text Available Abstract Purpose To evaluate the clinical efficacy and toxicity of stereotactic body radiation therapy (SBRT using extracranial gamma knife in patients with mainly bulky inoperable early stage non-small cell lung carcinoma (NSCLC. Materials and methods A total of 43 medically inoperable patients with mainly bulky Stage I/II NSCLC received SBRT using gamma knife were reviewed. The fraction dose and the total dose were determined by the radiation oncologist according to patients' general status, tumor location, tumor size and the relationship between tumor and nearby organ at risk (OAR. The total dose of 34~47.5 Gy was prescribed in 4~12 fractions, 3.5~10 Gy per fraction, one fraction per day or every other day. The therapeutic efficacy and toxicity were evaluated. Results The median follow-up was 22 months (range, 3-102 months. The local tumor response rate was 95.35%, with CR 18.60% (8/43 and PR 76.74% (33/43, respectively. The local control rates at 1, 2, 3, 5 years were 77.54%, 53.02%, 39.77%, and 15.46%, respectively, while the 1- and 2-year local control rates were 75% and 60% for tumor ≤3 cm; 84% and 71% for tumor sized 3~5 cm; 55% and 14.6% for tumor sized 5~7 cm; and 45%, 21% in those with tumor size of >7 cm. The overall survival rate at 1, 2, 3, 5 years were 92.04%, 78.04%, 62.76%, 42.61%, respectively. The toxicity of stereotactic radiation therapy was grade 1-2. Clinical stages were significantly important factor in local control of lung tumors (P = 0.000. Both clinical stages (P = 0.015 and chemotherapy (P = 0.042 were significantly important factors in overall survival of lung tumors. Conclusion SBRT is an effective and safe therapy for medically inoperable patients with early stage NSCLC. Clinical stage was the significant prognostic factors for both local tumor control and overall survival. The toxicity is mild. The overall local control for bulky tumors is poor. Tumor size is a poor prognostic factor, and the patients for

  1. Effet de la concentration du cuivre ou de l'argent sur les propriétés des agrégats de rhodium déposés sur silice amorphe dans l'hydrogénation du 1,3 butadiène

    Science.gov (United States)

    Ksibi, Z.; Ghorbel1, A.; Bellamy, B.

    1999-02-01

    Some samples with rhodium, rhodium-copper and rhodium-silver deposited on amorphous silica by vapor deposition of the metallic phase under high-vacuum (P silice amorphe par vapodéposition d'une phase métallique dans des conditions ultra-vide (P < 5.10-7 Pa) ont été préparés. L'effet de la taille des agrégats de rhodium ainsi que celui de l'addition du cuivre ou de l'argent sur les propriétés catalytiques du rhodium dans l'hydrogénation du 1,3 butadiène ont été étudiés. Les résultats montrent que la réaction étudiée est sensible à la taille des agrégats de rhodium et nous notons une différence importante entre l'effet du cuivre et de l'argent sur les propriétés du rhodium. En effet le cuivre forme un alliage avec le rhodium et provoque un effet poison d?où une modification de l'activité du métal noble, alors que l'argent exerce un effet de masque sur les particules de rhodium sans toutefois former d'alliage avec ce dernier.

  2. Coordination and organometallic chemistry of relevance to the rhodium-based catalyst for ethylene hydroamination.

    Science.gov (United States)

    Béthegnies, Aurélien; Kirkina, Vladislava A; Filippov, Oleg A; Daran, Jean-Claude; Belkova, Natalia V; Shubina, Elena; Polic, Rinaldo

    2011-12-19

    at the full QM level including solvation effects. The calculations confirm that the bridge splitting reaction is slightly less favorable for the iodido derivative. Overall, the study confirms the active role of rhodium(I) species in ethylene hydroamination catalyzed by RhCl(3)·3H(2)O/PPh(3)/nBu(4)PI and suggest that the catalyst resting state is [RhCl(PPh(3))(2)](2) or its C(2)H(4) adduct, RhCl(PPh(3))(2)(C(2)H(4)), under high ethylene pressure. PMID:22082087

  3. CATALYTIC INTERACTIONS OF RHODIUM, RUTHENIUM, AND MERCURY DURING SIMULATED DWPF CPC PROCESSING WITH HYDROGEN GENERATION

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D

    2008-10-09

    Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell (CPC) vessels were performed as part of the ongoing investigation into catalytic hydrogen generation. Rhodium, ruthenium, and mercury have been identified as the principal elemental factors affecting the peak hydrogen generation rate in the DWPF Sludge Receipt and Adjustment Tank (SRAT) for a given acid addition. The primary goal of this study is to identify any significant interactions between the three factors. Noble metal concentrations were similar to recent sludge batches. Rh ranged from 0.0026-0.013% and Ru ranged from 0.010-0.050% in the dried sludge solids, while initial Hg ranged from 0.5-2.5 wt%. An experimental matrix was developed to ensure that the existence of statistically significant two-way interactions could be determined without confounding of the main effects with the two-way interaction effects. The nominal matrix design consisted of twelve SRAT cycles. Testing included: a three factor (Rh, Ru, and Hg) study at two levels per factor (eight runs), two duplicate midpoint runs, and two additional replicate runs to assess reproducibility away from the midpoint. Midpoint testing can identify potential quadratic effects from the three factors. A single sludge simulant was used for all tests. Acid addition was kept effectively constant except to compensate for variations in the starting mercury concentration. Six Slurry Mix Evaporator (SME) cycles were performed to supplement the SME hydrogen generation database. Some of the preliminary findings from this study include: (1) Rh was linked to the maximum SRAT hydrogen generation rate in the first two hours after acid addition in preliminary statistical modeling. (2) Ru was linked conclusively to the maximum SRAT hydrogen generation rate in the last four hours of reflux in preliminary statistical modeling. (3) Increasing the ratio of Hg/Rh shifted the noble metal controlling the maximum SRAT hydrogen generation rate from

  4. Intercalation of heavy alkali metals (K, Rb and Cs) in the bundles of single wall nanotubes

    Science.gov (United States)

    Duclaux, L.; Méténier, K.; Lauginie, P.; Salvetat, J. P.; Bonnamy, S.; Beguin, F.

    2000-11-01

    The electric-arc discharge carbon deposits (collaret) containing Single Wall Carbon Nanotubes (SWNTs) were heat treated at 1600 °C during 2 days under N2 flow in order to eliminate the Ni catalyst by sublimation, without modifications of the SWNTs ropes. Sorting this deposit by gravity enabled to obtain in the coarsest particles higher amount of SWNTs ropes than in other particle sizes. The coarser particles of the carbon deposits were reacted with the alkali metals vapor giving intercalated samples with a MC8 composition. The intercalation led to an expansion of the 2D lattice of the SWNTs so that the alkali metals were intercalated in between the tubes within the bundles. Disordered lattices were observed after intercalation of Rb and Cs. The simulations of the X-ray diffractograms of SWNTs reacted with K, gave the best fit for three K ions occupying the inter-tubes triangular cavities. The investigations by EPR, and 13C NMR, showed that doped carbon deposits are metallic.

  5. Synthesis, characterization and dielectric properties of polynorbornadiene–clay nanocomposites by ROMP using intercalated Ruthenium catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Yalçınkaya, Esra Evrim, E-mail: esra.evrim.saka@ege.edu.tr; Balcan, Mehmet; Güler, Çetin

    2013-12-16

    Polynorbornadiene clay nanocomposites were prepared for the first time by the ring opening metathesis polymerization (ROMP) using modified montmorillonite and polynorbornadiene the latter of which is used commonly in electric–electronic industry. The Na–MMT clay was modified by a quaternary ammonium salt containing Ruthenium complex as a suitable catalyst and intercalant as well. The norbornadiene monomers were polymerized within the modified montmorillonite layers by in-situ polymerization method in different clay loading degrees. Intercalation ability of the Ru catalyst and partially exfoliated nanocomposite structure were proved by powder X-ray Diffraction (XRD) Spectroscopy and Transmission Electron Microscopy (TEM) methods. The nanocomposite materials with high thermal degradation temperature and low dielectric constant compared to the pure polynorbornadiene were obtained. The dielectric constants decreased with the increase of the clay content. - Highlights: • Polynorbornadiene–clay nanocomposites were prepared for the first time. • Ruthenium complex was assigned as both suitable catalyst and intercalant. • The norbornadiene was polymerized by in-situ polymerization method. • Exfoliation/intercalation structures were found to be related with loading degree. • PNBD–MMT nanocomposites had a higher thermal degradation temperature and lower dielectric constant.

  6. Influence of water contamination and conductive additives on the intercalation of lithium into graphite

    Energy Technology Data Exchange (ETDEWEB)

    Joho, F.; Rykart, B.; Novak, P. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Spahr, M.E.; Monnier, A. [Timcal AG, Sins (Switzerland)

    1999-08-01

    The irreversible charge loss in the first cycle of lithium intercalation into graphite electrodes for lithium-ion batteries is discussed as a function of water contamination of the electrolyte solution. Furthermore, the improvement of the electrode cycle life due to conductive additives to graphite is demonstrated. (author) 5 figs., 3 refs.

  7. Synthesis and characterization of montmorillonite clay intercalated with molecular magnetic compounds

    Science.gov (United States)

    Martins, Marcel G.; Martins, Daniel O. T. A.; de Carvalho, Beatriz L. C.; Mercante, Luiza A.; Soriano, Stéphane; Andruh, Marius; Vieira, Méri D.; Vaz, Maria G. F.

    2015-08-01

    In this work montmorillonite (MMT) clay, whose matrix was modified with an ammonium salt (hexadecyltrimethylammonium bromide - CTAB), was employed as an inorganic host for the intercalation of three different molecular magnetic compounds through ion exchange: a nitronyl nitroxide derivative 2-[4-(N-ethyl)-pyridinium]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (p-EtRad+) and two binuclear coordination compounds, [Ni(valpn)Ln]3+, where H2valpn stands for 1,3-propanediyl-bis(2-iminomethylene-6-methoxy-phenol), and Ln=GdIII; DyIII. The pristine MMT and the intercalated materials were characterized by X-ray powder diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and magnetic measurements. The X-ray diffraction data analysis showed an increase of the interlamellar space of the intercalated MMT, indicating the intercalation of the magnetic compounds. Furthermore, the magnetic properties of the hybrid compounds were investigated, showing similar behavior as the pure magnetic guest species.

  8. Electronic properties of Cs-intercalated single-walled carbon nanotubes derived from nuclear magnetic resonance

    Energy Technology Data Exchange (ETDEWEB)

    Abou-Hamad, E; Goze-Bac, C; Aznar, R [nanoNMRI group, UMR5587, Universite Montpellier II, Place E Bataillon, 34095 Montpellier Cedex 5 (France); Nitze, F; Waagberg, T [Department of Physics, Umeaa University, 90187 Umeaa (Sweden); Schmid, M; Mehring, M, E-mail: Thomas.wagberg@physics.umu.se [Physikalisches Institut, Universitaet Stuttgart, D-70569 Stuttgart (Germany)

    2011-05-15

    We report on the electronic properties of Cs-intercalated single-walled carbon nanotubes (SWNTs). A detailed analysis of the {sup 13}C and {sup 133}Cs nuclear magnetic resonance (NMR) spectra reveals an increased metallization of the pristine SWNTs under Cs intercalation. The 'metallization' of Cs{sub x}C materials where x=0-0.144 is evidenced from the increased local electronic density of states (DOS) n(E{sub F}) at the Fermi level of the SWNTs as determined from spin-lattice relaxation measurements. In particular, there are two distinct electronic phases called {alpha} and {beta} and the transition between these occurs around x=0.05. The electronic DOS at the Fermi level increases monotonically at low intercalation levels x<0.05 ({alpha}-phase), whereas it reaches a plateau in the range 0.05{<=}x{<=}0.143 at high intercalation levels ({beta}-phase). The new {beta}-phase is accompanied by a hybridization of Cs(6s) orbitals with C(sp{sup 2}) orbitals of the SWNTs. In both phases, two types of metallic nanotubes are found with a low and a high local n(E{sub F}), corresponding to different local electronic band structures of the SWNTs.

  9. Dynamic tuning of DNA-nanoparticle superlattices by molecular intercalation of double helix.

    Science.gov (United States)

    Pal, Suchetan; Zhang, Yugang; Kumar, Sanat K; Gang, Oleg

    2015-04-01

    Nanoparticle (NP) assembly using DNA recognition has emerged as a powerful tool for the fabrication of 3D superlattices. In addition to the vast structural diversity, this approach provides an avenue for dynamic 3D NP assembly, which is promising for the modulation of interparticle distances and, hence, for example, for in situ tuning of optical properties. While several approaches have been explored for changing NP separations in the lattices using responsiveness of single-stranded DNA (ss-DNA), far less work has been done for the manipulation of most abundant double-stranded DNA (ds-DNA) motifs. Here, we present a novel strategy for modulation of interparticle distances in DNA linked 3D self-assembled NP lattices by molecular intercalator. We utilize ethidium bromide (EtBr) as a model intercalator to demonstrate selective and isotropic lattice expansion for three superlattice types (bcc, fcc, and AlB2) due to the intercalation of ds-DNA linking NPs. We further show the reversibility of the lattice parameter using n-butanol as a retrieving agent as well as an increased lattice thermal stability by 12-14 °C due to the inclusion of EtBr. The proposed intercalator-based strategy permits the creation of reconfigurable and thermally stable superlattices, which could lead to tunable and functionally responsive materials.

  10. Standard Model for Superconductivity in Graphite Intercalation Compounds: Prediction of Optimum Tc

    Science.gov (United States)

    Takada, Yasutami

    2009-03-01

    Based on the model that was successfully applied to the explanation of superconductivity with the transition temperature Tc of about 0.1K or less in the alkali- intercalated graphite compounds such as KC8, RbC8, and CsC8 in 1982 [Y. Takada, J. Phys. Soc. Jpn. 51, 63 (1982) ], we have calculated Tc for the alkaline-earth- intercalated graphite compounds including CaC6, YbC6, and SrC6 with Tc of about 10K or less to find that the same model reproduces the observed Tc in those compounds as well, indicating that it is a standard model for superconductivity in the graphite intercalation compounds with Tc ranging over three orders of magnitude. The difference in Tc by two orders between KC8 and CaC6 can be accounted for by (i) doubling Z the valency of the metal ions, which enhances Tc by one order, and (ii) tripling m^* the effective mass of the superconducting three-dimensional electrons in the interlayer band, which also enhances Tc by one order. Enhancement of Tc well beyond 10 K is also predicted in this model, if intercalant metals are judiciously chosen so that both Z and m^* are increased further.

  11. Intercalation-controlled cyclodehydration of sorbitol in water over layered-niobium-molybdate solid acid.

    Science.gov (United States)

    Morita, Yuya; Furusato, Shogo; Takagaki, Atsushi; Hayashi, Shigenobu; Kikuchi, Ryuji; Oyama, S Ted

    2014-03-01

    Layered niobium molybdate (HNbMoO6 ) was used in the aqueous-phase dehydration of sorbitol and was found to exhibit remarkable selectivity toward its monomolecular-dehydrated intermediate 1,4-sorbitan. This was attributed to the selective intercalation of sorbitol within the interlayers with strong Brønsted acid sites.

  12. Sythesis of rare earth metal - GIC graphite intercalation compound in molten chloride system

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Masafumi; Hagiwara, Rika; Ito, Yasuhiko [Kyoto Univ. (Japan). Faculty of Engineering

    1994-07-01

    Graphite intercalation compounds of ytterbium and neodymium have been prepared by interacting graphite and metals in molten chlorides. These rare earth metals can be suspended in molten chlorides in the presence of trichlorides via disproportionation reaction RE(0) + RE(III) = 2RE(II) at lower than 300 degC. Carbides-free compounds are obtained in these systems. (author).

  13. Electronic properties and orbital-filling mechanism in Rb-intercalated copper phthalocyanine

    NARCIS (Netherlands)

    Evangelista, F.; Gotter, R.; Mahne, N.; Nannarone, S.; Ruocco, A.; Rudolf, P.

    2008-01-01

    The evolution of the electronic properties of a thin film of copper phthalocyanine deposited on Al(100) and progressively intercalated with rubidium atoms was followed by photoemission and X-ray absorption spectroscopies. Electron donation from the Rb atoms to the C32H16N8Cu molecules results in the

  14. Impact of Infralimbic Inputs on Intercalated Amygdale Neurons: A Biophysical Modeling Study

    Science.gov (United States)

    Li, Guoshi; Amano, Taiju; Pare, Denis; Nair, Satish S.

    2011-01-01

    Intercalated (ITC) amygdala neurons regulate fear expression by controlling impulse traffic between the input (basolateral amygdala; BLA) and output (central nucleus; Ce) stations of the amygdala for conditioned fear responses. Previously, stimulation of the infralimbic (IL) cortex was found to reduce fear expression and the responsiveness of Ce…

  15. Synthesis and characterization of organic intercalated layered double hydroxides and their application in bitumen modification

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Song [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China); Yu, Jianying, E-mail: jyyu@whut.edu.cn [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China); Sun, Yubin [Center for Materials Research and Analysis, Wuhan University of Technology, Wuhan 430070 (China); Wu, Shaopeng [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China)

    2015-02-15

    Organic layered double hydroxides (LDHs) intercalated by sodium dodecylbenzenesulfonate (SDBS) were prepared by anion-exchange method and applied to modify bitumen aiming at improving ageing resistance of bitumen. The organic LDHs (SDBS–LDHs) were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and Ultraviolet and visible (UV–vis) spectrophotometry. The effect of SDBS–LDHs and LDHs on physical and anti-ageing properties of bitumen was evaluated by means of conventional and rheological test. The results of XRD, FTIR and SEM show that SDBS is successfully intercalated into interlayer of LDHs, and the UV–vis reflectance and absorbance curves illustrate that intercalation of SDBS enhances the UV shielding effect of LDHs. The addition of SDBS–LDHs or LDHs has little influence on physical properties of bitumen because SDBS–LDHs and LDHs are physically mixed in bitumen. Compared with pristine bitumen after TFOT and UV irradiation ageing, the introduction of SDBS–LDHs and LDHs significantly improves thermal- and photo-oxidative ageing resistance of bitumen. Notably, bitumen with SDBS–LDHs exhibits better anti-ageing performance than that with LDHs, implying more effective modification of SDBS-LDHs which is due to the enhanced UV protective ability and compatibility with bitumen of SDBS–LDHs. - Highlights: • XRD, FTIR and SEM were used to confirm the successful intercalation. • SDBS–LDHs show superior UV protective ability. • SDBS–LDHs improved the anti-ageing properties of bitumen.

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

    Science.gov (United States)

    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.

  17. On the sequence selective bis-intercalation of a homodimeric thiazole orange dye in DNA

    DEFF Research Database (Denmark)

    Bunkenborg, Jakob; Stidsen, M M; Jacobsen, J P

    1998-01-01

    The thiazole orange dye 1,1'-(4,4,8,8-tetramethyl-4, 8-diazaundecamethylene)-bis-4-[(3-methyl-2,3-dihydro(benzo-1, 3-thiazolyl)-2-methylidene]quinolinium tetraiodide (TOTO) binds sequence selectively to double-stranded DNA (dsDNA) by bis-intercalation. Each chromophore is sandwiched between two...

  18. ORGANIC-INORGANIC HYBRIDS PREPARED FROM ALKYL PHOSPHONIUM SALTS INTERCALATED MONTMORILLONITES

    Directory of Open Access Journals (Sweden)

    SAHELI GANGULY

    2012-12-01

    Full Text Available Present investigation is focused on systematic and detailed characterization of alkyl phosphonium intercalated montmorillonite (MMT. The objective of the work is to provide a better understanding of the specific changes in properties of the hybrid material with changes in structure of incoming organic cations. In the present work, Na-MMT was intercalated with phosphonium salts of two different cationic head compositions namely alkyl triphenyl and alkyl tributyl groups. Length of alkyl chain was also varied. Resultant organic-inorganic hybrids were characterized by X-ray diffraction (XRD, Transmission electron microscopy (TEM, Thermogravimetry (TG and Fourier transformed infrared spectroscopy (FTIR. Effective volume occupied by the cationic heads influenced interlayer arrangements. Intercalated MMT with two different cationic heads behaved differently in relation to thermal decomposition patterns. Possible explanation was given based on hybridization of bonds. Van der Waals attachment of alkyl chains influenced the interlayer stacking and organic loading. Attempts were made to correlate the changes in properties of intercalated MMT with the structural aspects of incoming organic cations.

  19. Preparation of intercalated polyaniline/clay nanocomposite and its exfoliation exhibiting dendritic structure

    Indian Academy of Sciences (India)

    N Srivastava; Y Singh; R A Singh

    2011-07-01

    Intercalated composite of polyaniline and clay has been reported. The composite was prepared by in situ polymerization of aniline within the layers of `illite’ clay. The composite was characterized for its structural, spectral, and microscopic properties. At higher level of loading the layered structure of composite breaks forming exfoliated composite, revealing well-defined nanosized dendritic morphology of polyaniline.

  20. Optimal design of parallel triplex forming oligonucleotides containing Twisted Intercalating Nucleic Acids--TINA.

    Science.gov (United States)

    Schneider, Uffe V; Mikkelsen, Nikolaj D; Jøhnk, Nina; Okkels, Limei M; Westh, Henrik; Lisby, Gorm

    2010-07-01

    Twisted intercalating nucleic acid (TINA) is a novel intercalator and stabilizer of Hoogsteen type parallel triplex formations (PT). Specific design rules for position of TINA in triplex forming oligonucleotides (TFOs) have not previously been presented. We describe a complete collection of easy and robust design rules based upon more than 2500 melting points (T(m)) determined by FRET. To increase the sensitivity of PT, multiple TINAs should be placed with at least 3 nt in-between or preferable one TINA for each half helixturn and/or whole helixturn. We find that Delta T(m) of base mismatches on PT is remarkably high (between 7.4 and 15.2 degrees C) compared to antiparallel duplexes (between 3.8 and 9.4 degrees C). The specificity of PT by Delta T(m) increases when shorter TFOs and higher pH are chosen. To increase Delta Tms, base mismatches should be placed in the center of the TFO and when feasible, A, C or T to G base mismatches should be avoided. Base mismatches can be neutralized by intercalation of a TINA on each side of the base mismatch and masked by a TINA intercalating direct 3' (preferable) or 5' of it. We predict that TINA stabilized PT will improve the sensitivity and specificity of DNA based clinical diagnostic assays. PMID:20338879

  1. Optimal design of parallel triplex forming oligonucleotides containing Twisted Intercalating Nucleic Acids—TINA

    Science.gov (United States)

    Schneider, Uffe V.; Mikkelsen, Nikolaj D.; Jøhnk, Nina; Okkels, Limei M.; Westh, Henrik; Lisby, Gorm

    2010-01-01

    Twisted intercalating nucleic acid (TINA) is a novel intercalator and stabilizer of Hoogsteen type parallel triplex formations (PT). Specific design rules for position of TINA in triplex forming oligonucleotides (TFOs) have not previously been presented. We describe a complete collection of easy and robust design rules based upon more than 2500 melting points (Tm) determined by FRET. To increase the sensitivity of PT, multiple TINAs should be placed with at least 3 nt in-between or preferable one TINA for each half helixturn and/or whole helixturn. We find that ΔTm of base mismatches on PT is remarkably high (between 7.4 and 15.2°C) compared to antiparallel duplexes (between 3.8 and 9.4°C). The specificity of PT by ΔTm increases when shorter TFOs and higher pH are chosen. To increase ΔTms, base mismatches should be placed in the center of the TFO and when feasible, A, C or T to G base mismatches should be avoided. Base mismatches can be neutralized by intercalation of a TINA on each side of the base mismatch and masked by a TINA intercalating direct 3′ (preferable) or 5′ of it. We predict that TINA stabilized PT will improve the sensitivity and specificity of DNA based clinical diagnostic assays. PMID:20338879

  2. INTERCALATING TRIPLEXES AND DUPLEXES USING ARYL NAPHTHOIMIDAZOL AND PROCESS FOR THE PREPARATION THEREOF

    DEFF Research Database (Denmark)

    2009-01-01

    There is provided an intercalating oligonucleotide for stabilizing natural or modified DNA and RNA triplexes, duplexes and hybrids thereof having the general structure (I) triplex forming oligonucleotides of the invention are capable of binding specifically to double stranded target nucleic acids...

  3. Enhancement of electron-phonon coupling in Cs-overlayered intercalated bilayer graphene.

    Science.gov (United States)

    Kleeman, J; Sugawara, K; Sato, T; Takahashi, T

    2016-05-25

    We have performed high-resolution angle-resolved photoemission spectroscopy (ARPES) on cesium (Cs) intercalated bilayer graphene with a Cs overlayer (Cs-C8CsC8). Low-energy electron diffraction shows a (2  ×  2) pattern consistent with intercalation of a Cs layer similar to bulk C8Cs, in addition to the signature of a nearly commensurate superstructure created by the Cs overlayer. ARPES results reveal folding of the π bands due to the periodic (2  ×  2) potential of the intercalated Cs atoms, together with a free-electron-like state at the [Formula: see text] point. Significant mass renormalization is observed in the band dispersion near the Fermi level, indicative of strong electron-phonon coupling. Based on analysis of the self-energy, we find anisotropic electron-phonon coupling with an estimated strength of [Formula: see text]  ±  0.02 in the K-[Formula: see text] direction, and [Formula: see text] in the K-M direction. This coupling is much larger than that of other doped graphenes, and comparable to superconducting bulk GICs. We attribute this large electron-phonon coupling constant to the presence of the Cs overlayer, which highly dopes [Formula: see text] bands, and creates a structure similar to stage-I graphite intercalation compounds. PMID:27094681

  4. Temperature dependent local atomic displacements in ammonia intercalated iron selenide superconductor.

    Science.gov (United States)

    Paris, E; Simonelli, L; Wakita, T; Marini, C; Lee, J-H; Olszewski, W; Terashima, K; Kakuto, T; Nishimoto, N; Kimura, T; Kudo, K; Kambe, T; Nohara, M; Yokoya, T; Saini, N L

    2016-01-01

    Recently, ammonia-thermal reaction has been used for molecular intercalation in layered FeSe, resulting a new Lix(NH3)yFe2Se2 superconductor with Tc ~ 45 K. Here, we have used temperature dependent extended x-ray absorption fine structure (EXAFS) to investigate local atomic displacements in single crystals of this new superconductor. Using polarized EXAFS at Fe K-edge we have obtained direct information on the local Fe-Se and Fe-Fe bondlengths and corresponding mean square relative displacements (MSRD). We find that the Se-height in the intercalated system is lower than the one in the binary FeSe, suggesting compressed FeSe4 tetrahedron in the title system. Incidentally, there is hardly any effect of the intercalation on the bondlengths characteristics, revealed by the Einstein temperatures, that are similar to those found in the binary FeSe. Therefore, the molecular intercalation induces an effective compression and decouples the FeSe slabs. Furthermore, the results reveal an anomalous change in the atomic correlations across Tc, appearing as a clear decrease in the MSRD, indicating hardening of the local lattice mode. Similar response of the local lattice has been found in other families of superconductors, e.g., A15-type and cuprates superconductors. This observation suggests that local atomic correlations should have some direct correlation with the superconductivity.

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

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yi [Shandong Provincial Key Lab of Corrosion Science, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071 (China); Zhang, Dun, E-mail: zhangdun@qdio.ac.cn [Shandong Provincial Key Lab of Corrosion Science, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071 (China)

    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.

  6. Synthesis, characterization and properties of polyaniline/expanded vermiculite intercalated nanocomposite

    OpenAIRE

    Jianming Lin, Qunwei Tang, Jihuai Wu and Hui Sun

    2008-01-01

    The synthesis characterization and conductivities of polyaniline/expanded vermiculite intercalated nanocomposite are presented in this paper. The conductive emeraldine salt form of polyaniline is inserted into the interlayer of expanded vermiculite to produce the nanocomposite with high conductivity. The structures and properties are characterized by transmission electron microscopy x-ray diffraction spectroscopy fourier transform infrared spectroscopy thermogravimetry analysis and by the mea...

  7. Structure, molecular simulation, and release of aspirin from intercalated Zn-Al-layered double hydroxides.

    Science.gov (United States)

    Meng, Zilin; Li, Xiaowei; Lv, Fengzhu; Zhang, Qian; Chu, Paul K; Zhang, Yihe

    2015-11-01

    Aspirin or acetylsalicylic acid (AA), a non-steroidal anti-inflammatory drug, is intercalated into Zn-Al-layered double hydroxides (ZnAl-LDHs) by co-precipitation and reconstruction methods. The composition, structure, and morphology of the intercalated products as well as their release behavior are determined experimentally and theoretically by Material Studio 5.5. Experimental results disclose the strong interaction between the LDHs sheets and AA in the intercalated ZnAl-LDHs produced by co-precipitation and slow release of AA from the intercalated ZnAl-LDHs in both phosphate buffered saline (PBS) and borate buffered saline (BBS) solutions. The percentage of AA released from the ZnAl-LDHs prepared by both methods in PBS (96.87% and 98.12%) are much more than those in BBS (68.59% and 81.22%) implying that both H4BO4(-) and H2PO4(-) can exchange with AA in the ZnAl-LDHs. After AA is released to PBS, ZnAl-LDHs break into small pieces. The experimental results are explained theoretically based on the calculation of the bonding energy between the anions and LDHs sheets as well as the AlO bond length change in the LDHs sheets. PMID:26263219

  8. Electronic properties of Cs-intercalated single-walled carbon nanotubes derived from nuclear magnetic resonance

    KAUST Repository

    Abou-Hamad, E

    2011-05-24

    We report on the electronic properties of Cs-intercalated single-walled carbon nanotubes (SWNTs). A detailed analysis of the 13C and 133Cs nuclear magnetic resonance (NMR) spectra reveals an increased metallization of the pristine SWNTs under Cs intercalation. The \\'metallization\\' of CsxC materials where x=0–0.144 is evidenced from the increased local electronic density of states (DOS) n(EF) at the Fermi level of the SWNTs as determined from spin–lattice relaxation measurements. In particular, there are two distinct electronic phases called α and β and the transition between these occurs around x=0.05. The electronic DOS at the Fermi level increases monotonically at low intercalation levels x<0.05 (α-phase), whereas it reaches a plateau in the range 0.05≤x≤0.143 at high intercalation levels (β-phase). The new β-phase is accompanied by a hybridization of Cs(6s) orbitals with C(sp2) orbitals of the SWNTs. In both phases, two types of metallic nanotubes are found with a low and a high local n(EF), corresponding to different local electronic band structures of the SWNTs.

  9. Photoexcited triplet state provides a quantitative measure of intercalating drug-DNA binding energies

    Science.gov (United States)

    Maki, August H.; Alfredson, T. V.; Waring, M. J.

    1992-04-01

    A linear correlation between spectroscopic and thermodynamic properties of systems is rarely encountered. In triplet state ODMR studies of various DNA complexes of echinomycin, a quinoxaline-containing cyclic depsipeptide bis-intercalating antibiotic, and its biosynthesized quinoline analogs, such correlations are observed. The zero field splitting D-parameter of the intercalated quinoxaline or quinoline residue varies linearly with the free energy of drug-DNA complexing. From previous work, the DNA sequence specificity of echinomycin analogs is known to be influenced by the identity of the intercalating residue (e.g., quinoxaline vs. quinoline). The present results strongly suggest that the DNA sequence-specificity of these drugs is controlled largely by the intercalated residue, and that the energetics of the peptide- DNA interaction, although considerable, are relatively sequence independent. These conclusions run counter to the generally accepted idea that DNA recognition by sequence- seeking proteins is controlled by specific hydrogen bonding interactions. The high degree of N-methylation of the echinomycin peptide portion severely restricts these interactions, however. A simple theoretical model is presented to support the experimentally observed linear correlation between (Delta) D and (Delta) G.

  10. Band-gap engineering by Bi intercalation of graphene on Ir(111)

    Science.gov (United States)

    Warmuth, Jonas; Bruix, Albert; Michiardi, Matteo; Hänke, Torben; Bianchi, Marco; Wiebe, Jens; Wiesendanger, Roland; Hammer, Bjørk; Hofmann, Philip; Khajetoorians, Alexander A.

    2016-04-01

    We report on the structural and electronic properties of a single bismuth layer intercalated underneath a graphene layer grown on an Ir(111) single crystal. Scanning tunneling microscopy (STM) reveals a hexagonal surface structure and a dislocation network upon Bi intercalation, which we attribute to a √{3 }×√{3 }R 30∘ Bi structure on the underlying Ir(111) surface. Ab initio calculations show that this Bi structure is the most energetically favorable and illustrate that STM measurements are most sensitive to C atoms in close proximity to intercalated Bi atoms. Additionally, Bi intercalation induces a band gap (Eg=0.42 eV) at the Dirac point of graphene and an overall n doping (˜0.39 eV ) as seen in angular-resolved photoemission spectroscopy. We attribute the emergence of the band gap to the dislocation network which forms favorably along certain parts of the moiré structure induced by the graphene/Ir(111) interface.

  11. Concerted intercalation and minor groove recognition of DNA by a homodimeric thiazole orange dye

    DEFF Research Database (Denmark)

    Bunkenborg, Jakob; Gadjev, N I; Deligeorgiev, T;

    2000-01-01

    The thiazole orange dye TOTO binds to double-stranded DNA (dsDNA) by a sequence selective bis-intercalation. Each chromophore is sandwiched between two base pairs in a (5'-CpT-3'):(5'-ApG-3') site, and the linker spans two base pairs in the minor groove. We have used one- and two-dimensional NMR...

  12. Temperature dependent local atomic displacements in ammonia intercalated iron selenide superconductor

    Science.gov (United States)

    Paris, E.; Simonelli, L.; Wakita, T.; Marini, C.; Lee, J.-H.; Olszewski, W.; Terashima, K.; Kakuto, T.; Nishimoto, N.; Kimura, T.; Kudo, K.; Kambe, T.; Nohara, M.; Yokoya, T.; Saini, N. L.

    2016-01-01

    Recently, ammonia-thermal reaction has been used for molecular intercalation in layered FeSe, resulting a new Lix(NH3)yFe2Se2 superconductor with Tc ~ 45 K. Here, we have used temperature dependent extended x-ray absorption fine structure (EXAFS) to investigate local atomic displacements in single crystals of this new superconductor. Using polarized EXAFS at Fe K-edge we have obtained direct information on the local Fe-Se and Fe-Fe bondlengths and corresponding mean square relative displacements (MSRD). We find that the Se-height in the intercalated system is lower than the one in the binary FeSe, suggesting compressed FeSe4 tetrahedron in the title system. Incidentally, there is hardly any effect of the intercalation on the bondlengths characteristics, revealed by the Einstein temperatures, that are similar to those found in the binary FeSe. Therefore, the molecular intercalation induces an effective compression and decouples the FeSe slabs. Furthermore, the results reveal an anomalous change in the atomic correlations across Tc, appearing as a clear decrease in the MSRD, indicating hardening of the local lattice mode. Similar response of the local lattice has been found in other families of superconductors, e.g., A15-type and cuprates superconductors. This observation suggests that local atomic correlations should have some direct correlation with the superconductivity. PMID:27276997

  13. Preparation of Fe-intercalated Graphite Based on Coal Tailings, Dimensional Structure

    Directory of Open Access Journals (Sweden)

    Irfan Gustian

    2015-12-01

    Full Text Available Intercalated graphite from coal tailings have been modified through the intercalation of iron. Coal tailings which is a byproduct of the destruction process and flakes washing results from mining coal. Intercalation of iron goal is to improve the physical properties of graphite and modifying sizes of crystal lattice structure with thermal method. Modification process begins with the carbonization of coal tailings at 500ºC and activated with phosphoric acid. Activation process has done by pyrolysis at 700ºC. The results of pyrolysis was soaked in mineral oil for 24 hours, then pyrolysis again with variations in temperature 800°C and 900ºC for 1 hour and subsequent intercalation iron at 1% and 2%. Material before activated, after activated, and the results of pyrolysis still indicates order nano: 29, 25 and 36 nm respectively. X-ray diffraction characterization results indicate that change in the structure, the sizes crystal lattice structure of the material The greater the concentration of iron was added, the resulting peak at 2θ = 33 and 35 also will be more sharply. The results of SEM showed different morphologies from each treatment.

  14. Computational Procedure to Replace a Bulky Flywheel for a Process Machine by a Combination of Appropriately Controlled VVVf Drive for Motor and a Smaller Flywheel

    Directory of Open Access Journals (Sweden)

    Manjusha Viraj Palandurkar

    2012-06-01

    Full Text Available Process machines with tougher duty cycles are subjected to wide fluctuations in load torque. These often need a bulky flywheel for torque equalization with disadvantages of torsional oscillations. This results into fatigue of mechanical power transmission elements leading subsequently to equipment failure causing prolonged and frequent down time which results into financial losses. A simpler acceptable alternative is proposed in this article. Suitably monitored VVVf drives and low moment of inertia offer a much better alternative, for improving the system behavior drastically. Controlling the power input to the main electric drive with VVVf technique can generate almost matching demand torque characteristics. A much smaller flywheel is able to improve the accuracy to have better torque matching. This paper deals with estimation of necessary moment of inertia of flywheel in view of minimizing the difference in the required demand torque characteristics and the generated supply torque characteristics.

  15. Effect of bulky substituents on thiopyrylium polymethine aggregation in the solid state: A theoretical evaluation of the implications for all-optical switching applications

    KAUST Repository

    Gieseking, Rebecca L.

    2014-11-25

    Polymethine dyes in dilute solutions display many of the optical properties required for all-optical switching applications. However, in thin films, aggregation and polymethine-counterion interactions can substantially modify their properties and limit their utility. Here, we examine the impact of a series of bulky substituents on the solid-state molecular packing of thiopyrylium polymethines by using a theoretical approach combining molecular-dynamics simulations and quantum-chemical calculations. Importantly, it is found that the positions of the substituents near the center and/or ends of the dye determine the extent to which aggregation is reduced; in particular, substituents near the polymethine center primarily modify the type of aggregation that is observed, while substituents near the polymethine ends reduce aggregation and aid in maintaining solution-like properties in the solid state. Our theoretical study elucidates relationships between molecular structure and bulk optical properties and provides design guidelines for all-optical switching materials.

  16. Combined experimental and theoretical investigation of interactions between kaolinite inner surface and intercalated dimethyl sulfoxide

    International Nuclear Information System (INIS)

    Graphical abstract: Snapshot of the kaolinite–DMSO system after equilibrium is reached. - Highlights: • Dimethyl sulfoxide arranges a monolayer structure between kaolinite layers. • Weak hydrogen bonds exist between methyl groups of dimethyl sulfoxide and kaolinite silica layer. • Intercalated dimethyl sulfoxide forms strong hydrogen bonds with kaolinite alumina layer. - Abstract: Kaolinite intercalation complex with dimethyl sulfoxide (DMSO) was investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry–differential scanning calorimetry (TG–DSC) combined with molecular dynamics simulation. The bands assigned to the OH stretching of inner surface of kaolinite were significantly perturbed after intercalation of DMSO into kaolinite. Additionally, the bands attributed to the vibration of gibbsite-like layers of kaolinite shifted to the lower wave number, indicating that the intercalated DMSO were strongly hydrogen bonded to the alumina octahedral surface of kaolinite. The slightly decreased intensity of 1031 cm−1 and 1016 cm−1 band due to the in-plane vibration of Si−O of kaolinite revealed that some DMSO molecules formed weak hydrogen bonds with the silicon tetrahedral surface of kaolinite. Based on the TG result of kaolinite–DMSO intercalation complex, the formula of A12Si2O5(OH)4(DMSO)0.7 was obtained, with which the kaolinite–DMSO complex model was constructed. The molecular dynamics simulation of kaolinite–DMSO complex directly confirmed the monolayer structure of DMSO in interlayer space of kaolinite, where the DMSO arranged almost parallel with kaolinite basal surface with all methyl groups being distributed near the interlayer midplane and oxygen atoms orienting toward to the alumina octahedral surface. The radial distribution function between kaolinite and intercalated DMSO verified the strong hydrogen bonds forming between hydroxyl hydrogen atoms of alumina octahedral surface and

  17. Combined experimental and theoretical investigation of interactions between kaolinite inner surface and intercalated dimethyl sulfoxide

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuai [School of Geoscience and Surveying Engineering, China University of Mining & Technology, Beijing 100083 (China); Liu, Qinfu, E-mail: lqf@cumtb.edu.cn [School of Geoscience and Surveying Engineering, China University of Mining & Technology, Beijing 100083 (China); Cheng, Hongfei [School of Geoscience and Surveying Engineering, China University of Mining & Technology, Beijing 100083 (China); Zeng, Fangui [Department of Earth Science and Engineering, Taiyuan University of Technology, Taiyuan 030024 (China)

    2015-03-15

    Graphical abstract: Snapshot of the kaolinite–DMSO system after equilibrium is reached. - Highlights: • Dimethyl sulfoxide arranges a monolayer structure between kaolinite layers. • Weak hydrogen bonds exist between methyl groups of dimethyl sulfoxide and kaolinite silica layer. • Intercalated dimethyl sulfoxide forms strong hydrogen bonds with kaolinite alumina layer. - Abstract: Kaolinite intercalation complex with dimethyl sulfoxide (DMSO) was investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry–differential scanning calorimetry (TG–DSC) combined with molecular dynamics simulation. The bands assigned to the OH stretching of inner surface of kaolinite were significantly perturbed after intercalation of DMSO into kaolinite. Additionally, the bands attributed to the vibration of gibbsite-like layers of kaolinite shifted to the lower wave number, indicating that the intercalated DMSO were strongly hydrogen bonded to the alumina octahedral surface of kaolinite. The slightly decreased intensity of 1031 cm{sup −1} and 1016 cm{sup −1} band due to the in-plane vibration of Si−O of kaolinite revealed that some DMSO molecules formed weak hydrogen bonds with the silicon tetrahedral surface of kaolinite. Based on the TG result of kaolinite–DMSO intercalation complex, the formula of A1{sub 2}Si{sub 2}O{sub 5}(OH){sub 4}(DMSO){sub 0.7} was obtained, with which the kaolinite–DMSO complex model was constructed. The molecular dynamics simulation of kaolinite–DMSO complex directly confirmed the monolayer structure of DMSO in interlayer space of kaolinite, where the DMSO arranged almost parallel with kaolinite basal surface with all methyl groups being distributed near the interlayer midplane and oxygen atoms orienting toward to the alumina octahedral surface. The radial distribution function between kaolinite and intercalated DMSO verified the strong hydrogen bonds forming between hydroxyl hydrogen

  18. The intercalation reaction of 2,2'-bipyridine with layered compound MnPS3

    International Nuclear Information System (INIS)

    The intercalation process of 2,2'-bipyridine into layered MnPS3 is studied with powder X-ray powder diffraction (XRD) technology as the monitoring tool. From the XRD results, it is found that the absence or presence of acid greatly influences the existing form and the arranged orientation of the guest. Two series of the reactions are carried out. In Series A, only MnPS3 and 2,2'-bipyridine are present. While in Series B, a variety of acetic acid is added. During the intercalation of Series A, there coexist four phases: the 0 0 l phase (with lattice spacing of 6.47 A) is pristine MnPS3; the 0 0 l' phase (with lattice spacing of 9.81 A), indicating the parallel orientation of the 2,2'-bipyridine molecular ring to the layer; the 0 0 l'' phase (with lattice spacing of 12.20 A), indicating the perpendicular orientation of the 2,2'-bipyridine molecular ring to the layer of the host, which is only an intermediate phase for the formation of the 0 0 l''' phase; the 0 0 l''' phase (with the lattice spacing of 15.33 A), indicating the existence of the complex cation [Mn(bipy)3]2+ coming from the in situ coordination of the inserted guest with intralayered Mn2+ ions between the interlayer space of host. As the intercalation proceeds, the 0 0 l, 0 0 l' and 0 0 l'' phases finally disappear, and 0 0 l''' phase is intensified and a complete intercalate is obtained. In Series B, due to the presence of the acid, the formation of the complex cation [Mn(bipy)3]2+ is inhibited, and the amount of the acid in the intercalation plays a key role in the formation of the guest. With the increase of the acid, the protonated bipyridine becomes the main existing form of the guest, which is arranged in the perpendicular orientation of molecular ring to the layer. From the experimental evidences, the possible intercalation mechanisms are proposed and the novel intercalation phenomenon of in situ coordination of the inserted 2,2'-bipyridine with Mn2+ of the host is elucidated

  19. Simulated structural and magnetic behavior of Mn-Ti intercalated dichalcogenide crystals.

    Science.gov (United States)

    Roth, M W; Wandling, B; Kidd, T E; Shand, P M; Stollenwerk, A

    2016-05-11

    We present the results of extensive Monte Carlo simulations of intercalated manganese-titanium (Mn-Ti) layered TiS2 crystals. The computational model involves mixtures of Mn and Ti in various percentages placed on a triangular lattice with fixed lattice sites and up to five layers. The range of concentrations of intercalated Mn studied was 5%  ⩽  X Mn  ⩽  33% and for Ti, 0%  ⩽  X Ti  ⩽  15%, where X A denotes the percentage of the total number of lattice sites occupied by species A. The species are allowed to interact spatially through a screened Coulomb potential and magnetically with external and RKKY field terms. Structurally, the pure Mn systems present as disordered at very low densities and evolve through a 2  ×  2 structure (perfect at X Mn  =  25%) up to a [Formula: see text]  ×  [Formula: see text] lattice (perfect at X Mn  =  33%), with variations of the two 'perfect' lattice structures depending on density. Changes in density for pure Mn systems as well as those intercalated with both Mn and Ti dramatically affects the system's structural and magnetic properties, and the magnetic behavior of various morphological features present in the system are discussed. The RKKY interaction is adjusted based on the intercalant compositions and is very sensitive to structural variations in the intercalant layers. The composition ranges studied here encompass and exceed those that are experimentally accessible, which helps place experimentally relevant densities in perspective. PMID:27058645

  20. Simulated structural and magnetic behavior of Mn-Ti intercalated dichalcogenide crystals

    Science.gov (United States)

    Roth, M. W.; Wandling, B.; Kidd, T. E.; Shand, P. M.; Stollenwerk, A.

    2016-05-01

    We present the results of extensive Monte Carlo simulations of intercalated manganese-titanium (Mn-Ti) layered TiS2 crystals. The computational model involves mixtures of Mn and Ti in various percentages placed on a triangular lattice with fixed lattice sites and up to five layers. The range of concentrations of intercalated Mn studied was 5%  ⩽  X Mn  ⩽  33% and for Ti, 0%  ⩽  X Ti  ⩽  15%, where X A denotes the percentage of the total number of lattice sites occupied by species A. The species are allowed to interact spatially through a screened Coulomb potential and magnetically with external and RKKY field terms. Structurally, the pure Mn systems present as disordered at very low densities and evolve through a 2  ×  2 structure (perfect at X Mn  =  25%) up to a \\sqrt{3}   ×  \\sqrt{3} lattice (perfect at X Mn  =  33%), with variations of the two ‘perfect’ lattice structures depending on density. Changes in density for pure Mn systems as well as those intercalated with both Mn and Ti dramatically affects the system’s structural and magnetic properties, and the magnetic behavior of various morphological features present in the system are discussed. The RKKY interaction is adjusted based on the intercalant compositions and is very sensitive to structural variations in the intercalant layers. The composition ranges studied here encompass and exceed those that are experimentally accessible, which helps place experimentally relevant densities in perspective.

  1. Les trifluoro(organo)borates de potassium : nouvelles perspectives pour la formation de liaisons carbone-carbone à l'aide de complexes du rhodium

    OpenAIRE

    Pucheault, Mathieu

    2004-01-01

    This manuscript describes the use of potassium trifluoro(organo)borates in rhodiumcatalyzed carbon-carbon bond forming reactions. These easy to purify and very stable reagents turned out to constitute a valuable alternative to other boron reagents commonly used in transition metal catalyzed reactions. Asymmetric rhodium-catalyzed 1,4-additions of trifluoroborates were developed with the use of a chiral diphosphine which allowed a good control of the enantioselectivity. Under neutral condition...

  2. Oligomeric complexes of some heteroaromatic ligands and aromatic diamines with rhodium and molybdenum tetracarboxylates: 13C and 15N CPMAS NMR and density functional theory studies.

    Science.gov (United States)

    Leniak, Arkadiusz; Kamieński, Bohdan; Jaźwiński, Jarosław

    2015-05-01

    Seven new oligomeric complexes of 4,4'-bipyridine; 3,3'-bipyridine; benzene-1,4-diamine; benzene-1,3-diamine; benzene-1,2-diamine; and benzidine with rhodium tetraacetate, as well as 4,4'-bipyridine with molybdenum tetraacetate, have been obtained and investigated by elemental analysis and solid-state nuclear magnetic resonance spectroscopy, (13)C and (15)N CPMAS NMR. The known complexes of pyrazine with rhodium tetrabenzoate, benzoquinone with rhodium tetrapivalate, 4,4'-bipyridine with molybdenum tetrakistrifluoroacetate and the 1 : 1 complex of 2,2'-bipyridine with rhodium tetraacetate exhibiting axial-equatorial ligation mode have been obtained as well for comparison purposes. Elemental analysis revealed 1 : 1 complex stoichiometry of all complexes. The (15)N CPMAS NMR spectra of all new complexes consist of one narrow signal, indicating regular uniform structures. Benzidine forms a heterogeneous material, probably containing linear oligomers and products of further reactions. The complexes were characterized by the parameter complexation shift Δδ (Δδ = δcomplex  - δligand). This parameter ranged from around -40 to -90 ppm in the case of heteroaromatic ligands, from around -12 to -22 ppm for diamines and from -16 to -31 ppm for the complexes of molybdenum tetracarboxylates with 4,4'-bipyridine. The experimental results have been supported by a density functional theory computation of (15)N NMR chemical shifts and complexation shifts at the non-relativistic Becke, three-parameter, Perdew-Wang 91/[6-311++G(2d,p), Stuttgart] and GGA-PBE/QZ4P levels of theory and at the relativistic scalar and spin-orbit zeroth order regular approximation/GGA-PBE/QZ4P level of theory. Nucleus-independent chemical shifts have been calculated for the selected compounds. PMID:25614975

  3. New X-ray insight into oxygen intercalation in epitaxial graphene grown on 4H-SiC(0001)

    Energy Technology Data Exchange (ETDEWEB)

    Kowalski, G., E-mail: kowal@fuw.edu.pl; Tokarczyk, M. [Faculty of Physics, University of Warsaw, Hoża 69, 00-681 Warsaw (Poland); Dąbrowski, P.; Ciepielewski, P.; Możdżonek, M.; Strupiński, W. [Institute of Electronic Materials Technology, Wólczyńska 133, 01-919 Warsaw (Poland); Baranowski, J. M. [Faculty of Physics, University of Warsaw, Hoża 69, 00-681 Warsaw (Poland); Institute of Electronic Materials Technology, Wólczyńska 133, 01-919 Warsaw (Poland)

    2015-03-14

    Efficient control of intercalation of epitaxial graphene by specific elements is a way to change properties of the graphene. Results of several experimental techniques, such as X-ray photoelectron spectroscopy, micro-Raman mapping, reflectivity, attenuated total reflection, X-ray diffraction, and X-ray reflectometry, gave a new insight into the intercalation of oxygen in the epitaxial graphene grown on 4H-SiC(0001). These results confirmed that oxygen intercalation decouples the graphene buffer layer from the 4H-SiC surface and converts it into the graphene layer. However, in contrast to the hydrogen intercalation, oxygen does not intercalate between carbon planes (in the case of few layer graphene) and the interlayer spacing stays constant at the level of 3.35–3.32 Å. Moreover, X-ray reflectometry showed the presence of an oxide layer having the thickness of about 0.8 Å underneath the graphene layers. Apart from the formation of the nonuniform thin oxide layer, generation of defects in graphene caused by oxygen was also evidenced. Last but not least, water islands underneath defected graphene regions in both intercalated and non-intercalated samples were most probably revealed. These water islands are formed in the case of all the samples stored under ambient laboratory conditions. Water islands can be removed from underneath the few layer graphene stacks by relevant thermal treatment or by UV illumination.

  4. The Study of Surfaces' Micro- and Nanostructure on Interlayer Cleavages of InSe Layered Crystals Intercalated by Nickel

    Directory of Open Access Journals (Sweden)

    P.V. Galiy

    2016-03-01

    Full Text Available This paper presents the results of experimental study concerning element-phase composition, crystallographic structure, topography and electron-energy structure of interlayer cleavage (0001 surfaces, obtained for nickel intercalated (Ni3dInSe intercalate InSe layered crystals, by means of qualitative and quantitative X-ray photoelectron spectroscopy (XPS, low energy electron diffraction (LEED and scanning tunneling microscopy/spectroscopy (STM/STS. It was established that for all layered crystals' intercalates with different concentrations of nickel in initial synthesized InSe + x at.% Ni (x ≤ 10,0 % alloys and layered crystals further grown from them by Bridgman-Stockbarger method and subjected to intercalation, the maximum concentration of nickel on the cleavage (0001 surfaces of NiхInSe intercalates and, accordingly, in the interlayer gaps of up to 7.67 at. % is observed at 0.75 at. % of nickel in synthesized alloys. Nickel doesn't interact with selenium and indium and there are also no interaction with oxygen and carbon. It is established that nickel is placed in the interlayer gaps of NiхInSe intercalates and, accordingly, appears on the interlayer cleavage (0001 surfaces as fine-phase metal nickel clusters. The studied NiхInSe intercalate system is the perfect hybrid structure with the ability to use in magnetoelectronics.

  5. Ionic liquid ultrasound assisted dispersive liquid-liquid microextraction method for preconcentration of trace amounts of rhodium prior to flame atomic absorption spectrometry determination

    International Nuclear Information System (INIS)

    In this article, we consider ionic liquid based ultrasound-assisted dispersive liquid-liquid microextraction of trace amounts of rhodium from aqueous samples and show that this is a fast and reliable sample pre-treatment for the determination of rhodium ions by flame atomic absorption spectrometry. The Rh(III) was transferred into its complex with 2-(5-bromo-2-pyridylazo)-5-diethylamino phenol as a chelating agent, and an ultrasonic bath with the ionic liquid, 1-octyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide at room temperature was used to extract the analyte. The centrifuged rhodium complex was then enriched in the form of ionic liquid droplets and prior to its analysis by flame atomic absorption spectrometry, 300 μL ethanol was added to the ionic liquid-rich phase. Finally, the influence of various parameters on the recovery of Rh(III) was optimized. Under optimum conditions, the calibration graph was linear in the range of 4.0-500.0 ng mL-1, the detection limit was 0.37 ng mL-1 (3Sb/m, n = 7) and the relative standard deviation was ±1.63% (n = 7, C = 200 ng mL-1). The results show that ionic liquid based ultrasound assisted dispersive liquid-liquid microextraction, combined with flame atomic absorption spectrometry, is a rapid, simple, sensitive and efficient analytical method for the separation and determination of trace amounts of Rh(III) ions with minimum organic solvent consumption.

  6. Isomerisation and controlled condensation in an aqueous medium of allyl alcohol catalysed by new water-soluble rhodium complexes with 1,3,5-triaza-7-phosphaadamantane (PTA).

    Science.gov (United States)

    Smoleński, Piotr; Kirillova, Marina V; Guedes da Silva, M Fátima C; Pombeiro, Armando J L

    2013-08-14

    New aqua-soluble rhodium(I) [Rh(CO)(PTA)4]Cl (1) (PTA = 1,3,5-triaza-7-phosphaadamantane) and rhodium(III) [RhCl2(PTA)4]Cl (2) complexes have been synthesized via the reaction of [{Rh(CO)2(μ-Cl)}2] or RhCl3·3H2O, respectively, with stoichiometric amounts of PTA in ethanol. Compound 1 is also obtained upon reduction of 2 in an H2/CO atmosphere. They have been characterized by IR, (1)H and (31)P{H} NMR spectroscopies, elemental and single crystal X-ray diffraction analyses. While compound 1 shows distorted square-pyramid geometry (τ5 = 0.09) with a P3C-type basal plane, compound 2 is octahedral with the chloro ligands in the cis position. The hydride rhodium(I) complex [RhH(PTA)4] (3) is formed upon the addition of NaBH4 to an aqueous solution of 1 or 2. Compounds 1-3 (in the case of 2 upon reduction by H2) act as homogeneous catalysts, or catalyst precursors, in the isomerisation and condensation of allyl alcohol at room temperature and in an aqueous medium. The product selectivity is easily controlled by changing the concentration of the base in the reaction mixture, thus resulting in the exclusive formation of either 3-hydroxy-2-methylpentanal (HP) or 2-methyl-2-pentenal (MP) in quantitative yields. PMID:23793921

  7. Structures of Reactive Donor/Acceptor and Donor/Donor Rhodium Carbenes in the Solid State and Their Implications for Catalysis.

    Science.gov (United States)

    Werlé, Christophe; Goddard, Richard; Philipps, Petra; Farès, Christophe; Fürstner, Alois

    2016-03-23

    Owing to its tremendous preparative importance, rhodium carbene chemistry has been studied extensively during past decades. The invoked intermediates have, however, so far proved too reactive for direct inspection, and reliable experimental information has been extremely limited. A series of X-ray structures of pertinent intermediates of this type, together with supporting spectroscopic data, now closes this gap and provides a detailed picture of the constitution and conformation of such species. All complexes were prepared by decomposition of a diazoalkane precursor with an appropriate rhodium source; they belong to either the dirhodium(II) tetracarboxylate carbene series that enjoys widespread preparative use, or to the class of mononuclear half-sandwich carbenes of Rh(III), which show considerable potential. The experimental data correct or refine previous computational studies but corroborate the currently favored model for the prediction of the stereochemical course of rhodium catalyzed cyclopropanations, which is likely also applicable to other reactions. Emphasis is put on stereoelectronic rather than steric arguments, with the dipole of the acceptor substituent flanking the carbene center being the major selectivity determining factor. Moreover, the very subtle influence exerted by the anionic ligands on a Rh(III) center on the chemical character of the resulting carbenes species is documented by the structures of a homologous series of halide complexes. Finally, the isolation of a N-bonded Rh(II) diazoalkane complex showcases that steric hindrance represents an inherent limitation of the chosen methodology. PMID:26910883

  8. Environmentally benign graphite intercalation compound composition for exfoliated graphite, flexible graphite, and nano-scaled graphene platelets

    Science.gov (United States)

    Zhamu, Aruna; Jang, Bor Z.

    2014-06-17

    A carboxylic-intercalated graphite compound composition for the production of exfoliated graphite, flexible graphite, or nano-scaled graphene platelets. The composition comprises a layered graphite with interlayer spaces or interstices and a carboxylic acid residing in at least one of the interstices, wherein the composition is prepared by a chemical oxidation reaction which uses a combination of a carboxylic acid and hydrogen peroxide as an intercalate source. Alternatively, the composition may be prepared by an electrochemical reaction, which uses a carboxylic acid as both an electrolyte and an intercalate source. Exfoliation of the invented composition does not release undesirable chemical contaminants into air or drainage.

  9. Unforeseen high temperature and humidity stability of FeCl3 intercalated few layer graphene

    DEFF Research Database (Denmark)

    Wehenkel, Dominique Joseph; Bointon, Thomas Hardisty; Booth, Tim;

    2015-01-01

    We present the first systematic study of the stability of the structure and electrical properties of FeCl3 intercalated few-layer graphene to high levels of humidity and high temperature. Complementary experimental techniques such as electrical transport, high resolution transmission electron...... twice higher than the temperature at which the intercalation is conducted. The stability of FeCl3 intercalated few-layer graphene together with its unique values of low square resistance and high optical transparency, makes this material an attractive transparent conductor in future flexible electronic...

  10. Electrochemical Li-Ion Intercalation in Octacyanotungstate-Bridged Coordination Polymer with Evidence of Three Magnetic Regimes.

    Science.gov (United States)

    Long, Jérôme; Asakura, Daisuke; Okubo, Masashi; Yamada, Atsuo; Guari, Yannick; Larionova, Joulia

    2016-08-01

    Discovery of novel compounds capable of electrochemical ion intercalation is a primary step toward development of advanced electrochemical devices such as batteries. Although cyano-bridged coordination polymers including Prussian blue analogues have been intensively investigated as ion intercalation materials, the solid-state electrochemistry of the octacyanotungstate-bridged coordination polymer has not been investigated. Here, we demonstrate that an octacyanotungstate-bridged coordination polymer Tb(H2O)5[W(CN)8] operates as a Li(+)-ion intercalation electrode material. The detailed magnetic measurements reveal that the tunable amount of intercalated Li(+) ion in the solid-state redox reaction between paramagnetic [W(V)(CN)8](3-) and diamagnetic [W(IV)(CN)8](4-) in the framework enables the electrochemical control of different magnetic regimes. While the initial ferromagnetic long-range ordering is irreversibly lost upon lithium insertion, electrochemical switching between paramagnetic and short-range ordering regimes can be achieved.

  11. Electrochemical Li-Ion Intercalation in Octacyanotungstate-Bridged Coordination Polymer with Evidence of Three Magnetic Regimes.

    Science.gov (United States)

    Long, Jérôme; Asakura, Daisuke; Okubo, Masashi; Yamada, Atsuo; Guari, Yannick; Larionova, Joulia

    2016-08-01

    Discovery of novel compounds capable of electrochemical ion intercalation is a primary step toward development of advanced electrochemical devices such as batteries. Although cyano-bridged coordination polymers including Prussian blue analogues have been intensively investigated as ion intercalation materials, the solid-state electrochemistry of the octacyanotungstate-bridged coordination polymer has not been investigated. Here, we demonstrate that an octacyanotungstate-bridged coordination polymer Tb(H2O)5[W(CN)8] operates as a Li(+)-ion intercalation electrode material. The detailed magnetic measurements reveal that the tunable amount of intercalated Li(+) ion in the solid-state redox reaction between paramagnetic [W(V)(CN)8](3-) and diamagnetic [W(IV)(CN)8](4-) in the framework enables the electrochemical control of different magnetic regimes. While the initial ferromagnetic long-range ordering is irreversibly lost upon lithium insertion, electrochemical switching between paramagnetic and short-range ordering regimes can be achieved. PMID:27420412

  12. PREDICTION OF THE VISCOELASTIC PROPERTIES OF THE EQUIVALENT PARTICLE FOR THE INTERCALATED MULTI-LAYER STACK OF NANOPLASTICS

    Institute of Scientific and Technical Information of China (English)

    Weimin Zhang; Ping Zhang; Xuhui Deng; Chunyuan Zhang

    2007-01-01

    The aim of this paper is to apply the asymptotic homogenization method to determining analytically and numerically the transversely isotropic viscoelastic relaxation moduli of the equivalent particle for the intercalated multi-layer stack of intercalated type nanoplastics. A two-phase multilayered material containing n layers is considered. The matrix is assumed to be an isotropic viscoelastic standard linear body and the reinforcement is assumed to be an isotropic elastic body. Final explicit analytical formulae for the effective elastic moduli of the multilayered material are derived first; and then the correspondence principle is employed to obtain the homogenized relaxation moduli of the equivalent intercalated particle. A numerical example is given. Final explicit analytical formulae in the time domain derived here make it convenient to estimate the influence of all the particle parameters of micro-structural details on the effective properties of the equivalent intercalated particle. The results of this paper can also be applied to multi-layer composites.

  13. Bulkiness or aromatic nature of tyrosine-143 of actin is important for the weak binding between F-actin and myosin-ADP-phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Gomibuchi, Yuki [Graduate School of Science and Engineering, Teikyo University, Toyosatodai 1-1, Utsunomiya 320-8551 (Japan); Uyeda, Taro Q.P. [Biomedical Research Institute, National Institute of Advanced Industrial Science and Technology, AIST Tsukuba Central 4, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8562 (Japan); Wakabayashi, Takeyuki, E-mail: tw007@nasu.bio.teikyo-u.ac.jp [Graduate School of Science and Engineering, Teikyo University, Toyosatodai 1-1, Utsunomiya 320-8551 (Japan); Department of Judo Therapy, Faculty of Medical Technology, Teikyo University, Toyosatodai 1-1, Utsunomiya 320-8551 (Japan)

    2013-11-29

    Highlights: •The effect of mutation of Tyr143 that becomes more exposed on assembly was examined. •Mutation of tyrosine-143 of Dictyostelium actin changed actin polymerizability. •The bulkiness or aromatic nature of Tyr143 is important for the weak binding. •The weak interaction between myosin and actin strengthened by Tyr143Trp mutation. -- Abstract: Actin filaments (F-actin) interact with myosin and activate its ATPase to support force generation. By comparing crystal structures of G-actin and the quasi-atomic model of F-actin based on high-resolution cryo-electron microscopy, the tyrosine-143 was found to be exposed more than 60 Å{sup 2} to the solvent in F-actin. Because tyrosine-143 flanks the hydrophobic cleft near the hydrophobic helix that binds to myosin, the mutant actins, of which the tyrosine-143 was replaced with tryptophan, phenylalanine, or isoleucine, were generated using the Dictyostelium expression system. It polymerized significantly poorly when induced by NaCl, but almost normally by KCl. In the presence of phalloidin and KCl, the extents of the polymerization of all the mutant actins were comparable to that of the wild-type actin so that the actin-activated myosin ATPase activity could be reliably compared. The affinity of skeletal heavy meromyosin to F-actin and the maximum ATPase activity (V{sub max}) were estimated by a double reciprocal plot. The Tyr143Trp-actin showed the higher affinity (smaller K{sub app}) than that of the wild-type actin, with the V{sub max} being almost unchanged. The K{sub app} and V{sub max} of the Tyr143Phe-actin were similar to those of the wild-type actin. However, the activation by Tyr143Ile-actin was much smaller than the wild-type actin and the accurate determination of K{sub app} was difficult. Comparison of the myosin ATPase activated by the various mutant actins at the same concentration of F-actin showed that the extent of activation correlates well with the solvent-accessible surface areas (ASA

  14. Prediction of above 20 K superconductivity of blue phosphorus bilayer with metal intercalations

    Science.gov (United States)

    Zhang, Jun-Jie; Dong, Shuai

    2016-09-01

    First-principles calculations predicted monolayer blue phosphorus to be an alternative two-dimensional allotrope of phosphorus, like the recently discovered monolayer black phosphorus. Due to its unique crystalline and electronic structure, blue phosphorus may be a promising candidate as a BCS-superconductor after proper intercalation. In this study, using first-principles calculations, the favorable intercalation sites for some alkali metals and alkaline earths have been identified for Blue-P bilayer and the stacking configuration of bilayer is changed. Then the blue phosphorus bilayer transforms from a semiconductor to a metal due to the charge transfer from metal to phosphorus. Own to the strong electron–phonon coupling, isotropic superconducting state is induced and the calculated transition temperatures are 20.4, 20.1, and 14.4 K for Li-, Na-, and Mg-intercaltion, respectively, which is superior to other predicted or experimentally observed two-dimensional BCS-superconductors.

  15. Synthesis and intracrystalline oxidation of nitrite-intercalated layered double hydroxides

    International Nuclear Information System (INIS)

    Nitrite-intercalated LDHs could be prepared by a two-stage process that involves coprecipitation in the presence of nitrite ions followed by stirring the product with excess of nitrite ions. The nitrite ion lies flat in these LDHs with its c2-axis lying approximately perpendicular to the crystallographic c-axis. The interlayer nitrite ions in these LDHs could be quantitatively oxidized to nitrate ions using H2O2 solution. In the LDHs thus obtained the nitrate ion lies flat with its c3-axis parallel to the crystallographic c-axis (D3h symmetry) in the interlayer region resulting in lower basal spacing. - Graphical abstract: Nitrite-intercalated LDHs could be prepared by a two-stage process that involves coprecipitation in the presence of nitrite ions followed by stirring the product with excess of nitrite ions. The interlayer nitrite ions in these LDHs could be quantitatively oxidized to nitrate ions

  16. A theoretical study of a carbon lattice system for lithium intercalated carbon anodes

    Energy Technology Data Exchange (ETDEWEB)

    Scanlon, L.G.; Storch, D.M.; Newton, J.H. [Wright Lab., Wright-Patterson Air Force Base, OH (United States); Sandi, G. [Argonne National Lab., IL (United States)

    1997-09-01

    A theoretical study was performed using computational chemistry to describe the intermolecular forces between graphite layers as well as spacing and conformation. It was found that electron correlation and a diffuse basis set were important for this calculation. In addition, the high reactivity of edge sites in lithium intercalated carbon anodes was also investigated. In this case, the reactive sites appear to strongly correlate with the relative distribution of the total atomic spin densities as well as total atomic charges. The spacing of graphite layers and lithium ion separation within an {open_quotes}approximated{close_quotes} lithium intercalated carbon anode was also investigated. The spacing of the carbon layers used in this investigation agrees most closely for that found in disordered carbon lattices.

  17. Electrochemical Intercalation of Lithium into Raw and Mild Oxide-treated Carbon Nanotubes Prepared by CVD

    Institute of Scientific and Technical Information of China (English)

    LIN Ke-zhi; XU Yan-hui; WANG Xiao-lin; LUO Guo-hua

    2004-01-01

    The raw carbon nanotubes (CNTs) prepared by chemical vapor deposition (CVD) were used in electrochemical lithiation. To remove the impurity the mild oxidation was done on the samples. The electrochemical characteristics of the two samples are investigated by the galvanostatic charge-discharge measurements and cyclic voltammetry. The structural and interfacial changes of the CNTs electrode were analyzed by XRD and FT-IR. The samples show a reversibility of lithium intercalation and de-intercalation. The reversible capacities of the first five cycles are larger than 300 mAh/g and the irreversible capacity of the first cycle was much larger than that mentioned in literatures. There is no identical change in the structure during the charge and discharge. The reactions at the interface between electrode and the electrolyte are similar to those of other carbonaceous materials.

  18. Origin of the high p-doping in F intercalated graphene on SiC

    KAUST Repository

    Cheng, Y. C.

    2011-08-04

    The atomic and electronic structures of F intercalated epitaxialgraphene on a SiC(0001) substrate are studied by first-principles calculations. A three-step fluorination process is proposed. First, F atoms are intercalated between the graphene and the SiC, which restores the Dirac point in the band structure. Second, saturation of the topmost Si dangling bonds introduces p-doping up to 0.37 eV. Third, F atoms bond covalently to the graphene to enhance the p-doping. Our model explains the highly p-doped state of graphene on SiC after fluorination [A. L. Walter et al., Appl. Phys. Lett. 98, 184102 (2011)].

  19. Pseudo Dirac dispersion in Mn-intercalated graphene on SiC

    KAUST Repository

    Kahaly, Mousumi Upadhyay

    2013-07-01

    The atomic and electronic structures of bulk C6Mn, bulk C 8Mn, and Mn-intercalated graphene on SiC(0 0 0 1) and SiC(0001̄) are investigated by density functional theory. We find for both configurations of Mn-intercalated graphene a nonmagnetic state, in agreement with the experimental situation for SiC(0 0 0 1), and explain this property. The electronic structures around the Fermi energy are dominated by Dirac-like cones at energies consistent with data from angular resolved photoelectron spectroscopy [Gao et al., ACS Nano. 6 (2012) 6562]. However, our results demonstrate that the corresponding states trace back to hybridized Mn d orbitals, and not to the graphene. © 2013 Elsevier B.V. All rights reserved.

  20. Ordering in quasi-two-dimensional planar ferromagnets: A neutron scattering study of graphite intercalation compounds

    Science.gov (United States)

    Wiesler, D. G.; Suzuki, M.; Zabel, H.

    1987-11-01

    The magnetic ordering of stage-2 CoCl2- and NiCl2-graphite intercalation compounds (GIC's) has been investigated by neutron diffraction. Both of these compounds are observed to undergo a two-step ordering process. For temperatures within the range Tlsuccessive intercalate layers are translationally uncorrelated from each other. The in-plane peaks of CoCl2-GIC appear to have a shape characteristic of long-range spin order below Tl. However, the structure factor expected for a finite-sized bound vortex phase cannot at present be discounted for CoCl2-GIC. A similar scan at Tl

  1. 10th International School of Materials Science and Technology : Intercalation in Layered Materials "Ettore Majorana"

    CERN Document Server

    1986-01-01

    This volume is prepared from lecture notes for the course "Intercalation in Layered Materials" which was held at the Ettore Majorana Centre for Scientific Culture at Erice, Sicily in July, 1986, as part of the International School of Materials Science and Tech­ nology. The course itself consisted of formal tutorial lectures, workshops, and informal discussions. Lecture notes were prepared for the formal lectures, and short summaries of many of the workshop presentations were prepared. This volume is based on these lecture notes and research summaries. The material is addressed to advanced graduate students and postdoctoral researchers and assumes a background in basic solid state physics. The goals of this volume on Intercalation in Layered Materials include an introduc­ tion to the field for potential new participants, an in-depth and broad exposure for stu­ dents and young investigators already working in the field, a basis for cross-fertilization between workers on various layered host materials...

  2. A naproxen complex of dysprosium intercalates into calf thymus DNA base pairs

    Science.gov (United States)

    Yang, Mengsi; Jin, Jianhua; Xu, Guiqing; Cui, Fengling; Luo, Hongxia

    2014-01-01

    The binding mode and mechanism of dysprosium-naproxen complex (Dy-NAP) with calf thymus deoxyribonucleic acid (ctDNA) were studied using UV-vis and fluorescence spectra in physiological buffer (pH 7.4). The results showed that more than one type of quenching process occurred and the binding mode between Dy-NAP with ctDNA might be intercalation. In addition, ionic strength, iodide quenching and fluorescence polarization experiments corroborated the intercalation binding mode between Dy-NAP and ctDNA. The calculated thermodynamic parameters ΔG, ΔH and ΔS at different temperature demonstrated that hydrophobic interaction force played a major role in the binding process.

  3. Preparation and Characterization of Montmorillonite Intercalation Compounds with Quaternary Ammonium Surfactant: Adsorption Effect of Zearalenone

    Directory of Open Access Journals (Sweden)

    Yujin Li

    2014-01-01

    Full Text Available Montmorillonite (Mt was used as the original material to prepare intercalation compounds with quaternary ammonium surfactant (QAS. The adsorption of zearalenone (ZEA onto Mt and organomodified Mt was investigated in vitro. Effects of QAS in binding ZEA were studied. By the method of intercalation with dioctadecylmethylbenzylammonium chloride (DOMBAC, the sample exhibited the highest adsorption rate of ZEA (93.2% which was much higher than that of Mt (10.5%. Several methods were adopted to characterize samples, including XRD, TG/DSC, N2 adsorption/desorption, and FTIR. Adsorption isotherm parameters were obtained from Langmuir and Freundlich and the adsorption data fitted better to Langmuir. All results indicate that organomodified Mt has great potential to be a high-performance material to control ZEA contamination.

  4. Intercalation of pyridine and its derivatives into crystalline bismuth molybdenum hydrous oxide

    International Nuclear Information System (INIS)

    Bismuth molybdenum hydrous oxide was prepared by water-thermally direct precipitation in relatively concentrated solutions. The composition of the resulting product was Bi2Mo3O12 x 3.86 H2O determined by thermal analysis and ICP. The X-ray powder diffraction patterns of the crystal synthesized was identical with that of Bi2Mo3O12 x 4.75 H2O. Pyridine, 2,5-dimethylpyridine and 4-benzylpiridine were intercalated into inorganic crystal, significantly expanding interlayer distance along b axis in the monoclinic cell unit of bismuth molybdenum hydrous oxide. The organic molecules were intercalated by solvent exchange mechanism which mainly devoted to the expansion of interlayer spacing. (author)

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

    Science.gov (United States)

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

    2015-12-01

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

  6. Synchrotron-Radiation X-Ray Investigation of Li+/Na+ Intercalation into Prussian Blue Analogues

    Directory of Open Access Journals (Sweden)

    Yutaka Moritomo

    2013-01-01

    Full Text Available Prussian blue analogies (PBAs are promising cathode materials for lithium ion (LIB and sodium ion (SIB secondary batteries, reflecting their covalent and nanoporous host structure. With use of synchrotron-radiation (SR X-ray source, we investigated the structural and electronic responses of the host framework of PBAs against Li+ and Na+ intercalation by means of the X-ray powder diffraction (XRD and X-ray absorption spectroscopy (XAS. The structural investigation reveals a robust nature of the host framework against Li+ and Na+ intercalation, which is advantageous for the stability and lifetime of the batteries. The spectroscopic investigation identifies the redox processes in respective plateaus in the discharge curves. We further compare these characteristics with those of the conventional cathode materials, such as, LiCoO2, LiFePO4, and LiMn2O4.

  7. Intercalation of Varied Sulfonates into a Layered MOC: Confinement-Caused Tunable Luminescence and Novel Properties.

    Science.gov (United States)

    Wen, Yuehong; Sheng, Tianlu; Zhu, Xiaoquan; Zhang, Hao; Zhuo, Chao; Hu, Shengmin; Cao, Wenhai; Wu, Xintao

    2016-04-01

    The pores/channels of porous 3D metal-organic frameworks (MOFs) have been widely applied to incorporate gas, solvent, or organic molecules. On the contrary, the utilization of the interlamellar void of layered metal-organic complexes (MOCs) remains underappreciated, although it is more flexible and available to accommodate molecules with different sizes. In this work, diverse sulfonates have been intercalated purposely into an identical layered MOC, which constructed various novel intercalation compounds possessing fluorescent, white-light emitting, photochromic, homochiral, or nonlinear optical (NLO) properties. With the help of single-crystal X-ray diffraction, their structures and the mutual interactions between the MOC host and the sulfonate guests were characterized. The properties of the guest molecules were tuned and meanwhile some new performances were generated after confining them into the interlayer region. Such a hybrid approach provides an efficient strategy to design and prepare multifunctional materials. PMID:26919304

  8. Optical and structural effects of aniline intercalation in PbI2

    Science.gov (United States)

    Mehrotra, Vivek; Lombardo, S.; Thompson, Michael O.; Giannelis, Emmanuel P.

    1991-09-01

    Aniline has been intercalated in lead iodide thin films by exposure to aniline vapors in an evacuated chamber. X-ray diffraction and Raman spectroscopy have confirmed the presence of aniline in the interlayer space of PbI2. Intercalation leads to an increase of 0.5 eV in the optical band gap. The large increase in the band gap can be modeled by computing changes in the band structure resulting from the electrostatic interaction of the -NH2 dipole of aniline with the iodine 5pz electron. This interaction lowers and flattens the valence band along the ΓA direction. The band-gap increase, calculated for various possible configurations of the aniline molecule, is in the range 0.35-0.57 eV.

  9. Intercalation of graphene on SiC(0001) via ion implantation

    Science.gov (United States)

    Stöhr, Alexander; Forti, Stiven; Link, Stefan; Zakharov, Alexei A.; Kern, Klaus; Starke, Ulrich; Benia, Hadj M.

    2016-08-01

    Electronic devices based on graphene technology are catching on rapidly and the ability to engineer graphene properties at the nanoscale is becoming, more than ever, indispensable. Here, we present a procedure of graphene functionalization on SiC(0001) that paves the way towards the fabrication of complex graphene electronic chips. The procedure resides on the well-known ion-implantation technique. The efficiency of the working principle is demonstrated by the intercalation of the epitaxial graphene layer on SiC(0001) with Bi atoms, which was not possible following standard procedures. The investigation of the obtained graphene system reveals no clear spin-orbit coupling enhancement expected by theory in addition to the presence of residual structural defects. Our graphene/SiC(0001) intercalation procedure puts forward the ion-beam lithography to nanostructure and functionalize desired graphene chips.

  10. Forces generated by cell intercalation tow epidermal sheets in mammalian tissue morphogenesis.

    Science.gov (United States)

    Heller, Evan; Kumar, K Vijay; Grill, Stephan W; Fuchs, Elaine

    2014-03-31

    While gastrulation movements offer mechanistic paradigms for how collective cellular movements shape developing embryos, far less is known about coordinated cellular movements that occur later in development. Studying eyelid closure, we explore a case where an epithelium locally reshapes, expands, and moves over another epithelium. Live imaging, gene targeting, and cell-cycle inhibitors reveal that closure does not require overlying periderm, proliferation, or supracellular actin cable assembly. Laser ablation and quantitative analyses of tissue deformations further distinguish the mechanism from wound repair and dorsal closure. Rather, cell intercalations parallel to the tissue front locally compress it perpendicularly, pulling the surrounding epidermis along the closure axis. Functional analyses in vivo show that the mechanism requires localized myosin-IIA- and α5β1 integrin/fibronectin-mediated migration and E-cadherin downregulation likely stimulated by Wnt signaling. These studies uncover a mode of epithelial closure in which forces generated by cell intercalation are leveraged to tow the surrounding tissue. PMID:24697897

  11. Secondary ion mass spectroscopy depth profiling of hydrogen-intercalated graphene on SiC

    Science.gov (United States)

    Michałowski, Paweł Piotr; Kaszub, Wawrzyniec; Merkulov, Alexandre; Strupiński, Włodek

    2016-07-01

    For a better comprehension of hydrogen intercalation of graphene grown on a silicon carbide substrate, an advanced analytical technique is required. We report that with a carefully established measurement procedure it is possible to obtain a reliable and reproducible depth profile of bi-layer graphene (theoretical thickness of 0.69 nm) grown on the silicon carbide substrate by the Chemical Vapor Deposition method. Furthermore, we show that with depth resolution as good as 0.2 nm/decade, both hydrogen coming from the intercalation process and organic contamination can be precisely localized. As expected, hydrogen was found at the interface between graphene and the SiC substrate, while organic contamination was accumulated on the surface of graphene and did not penetrate into it. Such a precise measurement may prove to be invaluable for further characterization of 2D materials.

  12. Synthesis and Characterization of Self-Assembled V2O5 Mesostructures Intercalated by Polyaniline

    Institute of Scientific and Technical Information of China (English)

    Li Li; Zifeng Yan

    2005-01-01

    A new nanocomposite of vanadium pentoxide (V2O5) and polyaniline (PANI) were synthesized by in situ oxidative polymerization/intercalation on V2O5 powder at room temperature. The reaction was facile and topotactic, forming polyaniline as the emeraldine salt. It was indicated that V2O5 itself can catalyze the oxidative polymerization of aniline and that layered structure could make aniline intercalate into the V2O5 framework. It makes the in situ polymerization feasible to occur in the layer of V2O5 structure. XRD results showed PANI/V2O5 nanocomposite possessed lamellar mesostructure, which was determined by an X-ray diffraction peak at 6.5° and SEM photograph. And FT-IR spectrum suggested that there was interaction between PANI and V2O5. The hybrid had better thermal stability in N2 and air ambience.

  13. Study on the supramolecular structure of sorbic acid intercalated Zn-Al layered double hydroxides and its thermal decomposition

    Institute of Scientific and Technical Information of China (English)

    MENG Jinhong; ZHANG Hui; David G. Evans; DUAN Xue

    2005-01-01

    A novel organic-inorganic composite, sorbic acid intercalated zinc aluminum layered double hydroxides (SA-ZnAl-LDHs) has been successfully assembled by a simple direct coprecipitation method. A holistic approach including normal XRD, FT-IR, and UV-Vis measurements and simultaneous TG/DTA/MS and in situ HT-XRD techniques was employed to explore the supramolecular intercalation structure and the thermal decomposition properties of as-synthesized SA-ZnAl-LDHs material.

  14. Capture of a Transition State Using Molecular Dynamics: Creation of an Intercalation Site in dsDNA with Ethidium Cation

    Directory of Open Access Journals (Sweden)

    Regina R. Monaco

    2010-01-01

    Full Text Available The mechanism of intercalation and the ability of double stranded DNA (dsDNA to accommodate a variety of ligands in this manner has been well studied. Proposed mechanistic steps along this pathway for the classical intercalator ethidium have been discussed in the literature. Some previous studies indicate that the creation of an intercalation site may occur spontaneously, with the energy for this interaction arising either from solvent collisions or soliton propagation along the helical axis. A subsequent 1D diffusional search by the ligand along the helical axis of the DNA will allow the ligand entry to this intercalation site from its external, electrostatically stabilized position. Other mechanistic studies show that ethidium cation participates in the creation of the site, as a ligand interacting closely with the external surface of the DNA can cause unfavorable steric interactions depending on the ligands' orientation, which are relaxed during the creation of an intercalation site. Briefly, such a site is created by the lengthening of the DNA molecule via bond rotation between the sugars and phosphates along the DNA backbone, causing an unwinding of the dsDNA itself and separation between the adjacent base pairs local to the position of the ligand, which becomes the intercalation site. Previous experimental measurements of this interaction measure the enthalpic cost of this part of the mechanism to be about −8 kcal/mol. This paper reports the observation, during a computational study, of the spontaneous opening of an intercalation site in response to the presence of a single ethidium cation molecule in an externally bound configuration. The concerted motions between this ligand and the host, a dsDNA decamer, are clear. The dsDNA decamer AGGATGCCTG was studied; the central …GATG… site was the intercalation site.

  15. Renal Type A Intercalated Cells Contain Albumin in Organelles with Aldosterone-Regulated Abundance

    OpenAIRE

    Jensen, Thomas Buus; Cheema, Muhammad Umar; Szymiczek, Agata; Damkier, Helle Hasager; Praetorius, Jeppe

    2015-01-01

    Albumin has been identified in preparations of renal distal tubules and collecting ducts by mass spectrometry. This study aimed to establish whether albumin was a contaminant in those studies or actually present in the tubular cells, and if so, identify the albumin containing cells and commence exploration of the origin of the intracellular albumin. In addition to the expected proximal tubular albumin immunoreactivity, albumin was localized to mouse renal type-A intercalated cells and cells i...

  16. Electron beam induced electronic transport in alkyl amine-intercalated VOx nanotubes

    OpenAIRE

    O'Dwyer, Colm; Lavayen, Vladimir; Clavijo-Cedeno, C.; Sotomayor Torres, Clivia M.

    2008-01-01

    The electron beam induced electronic transport in primary alkyl amine-intercalated V2O5 nanotubes is investigated where the organic amine molecules are employed as molecular conductive wires to an aminosilanized substrate surface and contacted to Au interdigitated electrode contacts. The results demonstrate that the high conductivity of the nanotubes is related to the non-resonant tunnelling through the amine molecules and a reduced polaron hopping conduction through the vanadium oxide itself...

  17. Noble-metal intercalation process leading to a protected adatom in a graphene hollow site

    Science.gov (United States)

    Narayanan Nair, M.; Cranney, M.; Jiang, T.; Hajjar-Garreau, S.; Aubel, D.; Vonau, F.; Florentin, A.; Denys, E.; Bocquet, M.-L.; Simon, L.

    2016-08-01

    In previous studies, we have shown that gold deposited on a monolayer (ML) of graphene on SiC(0001) is intercalated below the ML after an annealing procedure and affects the band structure of graphene. Here we prove experimentally and theoretically that some of the gold forms a dispersed phase composed of single adatoms, being intercalated between the ML and the buffer layer and in a hollow position with respect to C atoms of the ML on top. They are freestanding and negatively charged, due to the partial screening of the electron transfer between SiC and the ML, without changing the intrinsic n-type doping of the ML. As these single atoms decouple the ML from the buffer layer, the quasiparticles of graphene are less perturbed, thus increasing their Fermi velocity. Moreover, the hollow position of the intercalated single Au atoms might lead to spin-orbit coupling in the graphene layer covering IC domains. This effect of spin-orbit coupling has been recently observed experimentally in Au-intercalated graphene on SiC(0001) [D. Marchenko, A. Varykhalov, J. Sánchez-Barriga, Th. Seyller, and O. Rader, Appl. Phys. Lett. 108, 172405 (2016), 10.1063/1.4947286] and has been theoretically predicted for heavy atoms, like thallium, in a hollow position on graphene [C. Weeks, J. Hu, J. Alicea, M. Franz, and R. Wu, Phys. Rev. X 1, 021001 (2011), 10.1103/PhysRevX.1.021001; A. Cresti, D. V. Tuan, D. Soriano, A. W. Cummings, and S. Roche, Phys. Rev. Lett. 113, 246603 (2014), 10.1103/PhysRevLett.113.246603].

  18. Recognition of Anhydrite Intercalated Salt Deposit from Seismic Dataset Distorted by Noise

    Directory of Open Access Journals (Sweden)

    Kawalec-Latała Ewa

    2015-09-01

    Full Text Available Acoustic inversion is useful to extract information from seismic data. Inhomogeneities of salt deposits should be predicted before the decision of underground storage location is made. The work concerns the possibility of detecting anhydrite intercalation in the rock salt from seismic dataset. The resolution strongly depends on signal to noise ratio. The synthetic pseudoacoustic impedance sections are generated for efficiency test of predictive and minimum entropy deconvolution process, when random noise distorts the seismic traces.

  19. A twist-bend nematic to an intercalated, anticlinic, biaxial phase transition in liquid crystal bimesogens.

    Science.gov (United States)

    Mandle, Richard J; Goodby, John W

    2016-02-01

    In this article we describe for bimesogens the first observed transition from a "heliconical" twist-bend nematic liquid crystal to a novel biaxial, anticlinic, intercalated lamellar phase. The phase behaviour and structures of both polymorphs is similar to that of polymers, confirming that bimesogens can act as model systems for main chain liquid crystal polymers, and in principle are separate soft-matter branches of self-organising systems. PMID:26626825

  20. Intercalation between antitumor anthracyclines and DNA as probed by resonance and surface-enhanced Raman spectroscopy

    Science.gov (United States)

    Smulevich, G.; Mantini, A. R.; Casu, M.; Marzocchi, M. P.

    1991-05-01

    The antiturnor anthracyclincs, idarubicin (IDA ), adrianiycin (ADM), epirubicin (EPI), carminomycin (CAR) and 1 1-deoxycarminornycin (DCM), whose siructural formula includes a substituted hydroxyanthraquirionc chrornophore and a sugar residue, form intercalation complexes with DNA. The stacking interaction between the chromophore and the base-pairs of DNA gives rise to noticeable ciTects on resonance Raman (RR) and surface-enhanced resonance Raman (SERRS) scattering as well as on the absorption (ABS), its second derivative (D2) and fluorescence emission (FEM) spectra.

  1. Efficient dechlorination of carbon tetrachloride by hydrophobic green rust intercalated with dodecanoate anions

    DEFF Research Database (Denmark)

    Ayala Luis, Karina Barbara; Ginette Anneliese Cooper, Nicola; Bender Koch, Christian;

    2012-01-01

    The reductive dechlorination of carbon tetrachloride (CT) by Fe-II-Fe-III hydroxide (green rust) intercalated with dodecanoate, (Fe4Fe2III)-Fe-II (OH)(12)(C12H23O2)(2)center dot gamma H2O (designated GR(C12)), at pH similar to 8 and at room temperature was investigated. CT at concentration levels...

  2. Intermolecular interactions between imidazole derivatives intercalated in layered solids. Substituent group effect

    International Nuclear Information System (INIS)

    This study sheds light on the intermolecular interactions between imidazole derive molecules (2-methyl-imidazole, 2-ethyl-imidazole and benzimidazole) intercalated in T[Ni(CN)4] layers to form a solid of formula unit T(ImD)2[Ni(CN)4]. These hybrid inorganic–organic solids were prepared by soft chemical routes and their crystal structures solved and refined from X-ray powder diffraction data. The involved imidazole derivative molecules were found coordinated through the pyridinic N atom to the axial positions for the metal T in the T[Ni(CN)4] layer. In the interlayers region ligand molecules from neighboring layers remain stacked in a face-to-face configuration through dipole–dipole and quadrupole–quadrupole interactions. These intermolecular interactions show a pronounced dependence on the substituent group and are responsible for an ImD-pillaring concatenation of adjacent layers. This is supported by the structural information and the recorded magnetic data in the 2–300 K temperature range. The samples containing Co and Ni are characterized by presence of spin–orbit coupling and pronounced temperature dependence for the effective magnetic moment except for 2-ethyl-imidazole related to the local distortion for the metal coordination environment. For this last one ligand a weak ferromagnetic ordering ascribed to a super-exchange interaction between T metals from neighboring layers through the ligands π–π interaction was detected. - Graphical abstract: In the interlayers region imidazole derivative molecules are oriented according to their dipolar and quadrupolar interactions and minimizing the steric impediment. Highlights: • Imidazole derivatives intercalation compounds. • Intermolecular interaction between intercalated imidazole derivatives. • Hybrid inorganic–organic solids. • Pi–pi interactions and ferromagnetic coupling. • Dipolar and quadrupolar interactions between intercalated imidazole derivatives

  3. Sub-nanometer control of the interlayer spacing in thin films of intercalated rodlike conjugated molecules.

    Science.gov (United States)

    Vogel, Jörn-Oliver; Salzmann, Ingo; Opitz, Ricarda; Duhm, Steffen; Nickel, Bert; Rabe, Jürgen P; Koch, Norbert

    2007-12-27

    Organic molecular beam co-deposition of rodlike conjugated molecules with an alkylated analogue resulted in thin film structures with layers of alternating semiconducting (conjugated molecular parts) and insulating (alkyl parts) character. By varying the alkylated molecule ratio, we could adjust the distance between conjugated layers with sub-nanometer precision, exploiting the mechanical flexibility of the alkyl chains. Furthermore, due to mutual molecular intercalation, mixed layers containing two conjugated moieties with vastly different electronic properties could be fabricated.

  4. Synthesis and Characterization of Graphene Thin Films by Chemical Reduction of Exfoliated and Intercalated Graphite Oxide

    OpenAIRE

    Thema, F. T.; M. J. Moloto; E. D. Dikio; Nyangiwe, N. N.; L. Kotsedi; Maaza, M.; Khenfouch, M.

    2013-01-01

    Commercial flakes of graphite were prepared into functionalized graphene oxide (GO) by chemical treatment. After the exfoliation and intercalation of graphene into functionalized graphene oxide that formed stable colloidal dispersion in polar aprotic solvent, the reduction process was undertaken by continuous stirring with hydrazine hydrate. The reduced material was characterized by X-ray diffraction (XRD), attenuated total reflectance (ATR) FT-IR, ultraviolet visible (UV-vis), atomic force m...

  5. Use of Propranolol-Magnesium Aluminium Silicate Intercalated Complexes as Drug Reservoirs in Polymeric Matrix Tablets

    OpenAIRE

    T. Pongjanyakul; S Rojtanatanya

    2012-01-01

    The objective of the present study was to investigate the use of propranolol-magnesium aluminium silicate intercalated complexes as drug reservoirs in hydroxypropylmethylcellulose tablets. The matrix tablets containing the complexes were prepared and characterised with respect to propranolol release and were subsequently compared with those loading propranolol or a propranolol-magnesium aluminium silicate physical mixture. Additionally, the effects of varying viscosity grades of hydroxypropyl...

  6. Anthocyanin Interactions with DNA: Intercalation, Topoisomerase I Inhibition and Oxidative Reactions

    OpenAIRE

    Webb, Michael R.; Min, Kyungmi; Susan E. Ebeler

    2008-01-01

    Anthocyanins and their aglycone anthocyanidins are pigmented flavonoids found in significant amounts in many commonly consumed foods. They exhibit a complex chemistry in aqueous solution, which makes it difficult to study their chemistry under physiological conditions. Here we used a gel electrophoresis assay employing supercoiled DNA plasmid to examine the ability of these compounds (1) to intercalate DNA, (2) to inhibit human topoisomerase I through both inhibition of plasmid relaxation act...

  7. Intermolecular interactions between imidazole derivatives intercalated in layered solids. Substituent group effect

    Energy Technology Data Exchange (ETDEWEB)

    González, M.; Lemus-Santana, A.A. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México, DF (Mexico); Rodríguez-Hernández, J. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México, DF (Mexico); Instituto de Ciencia y Tecnología de Materiales, Universidad de La Habana, Havana (Cuba); Aguirre-Velez, C.I. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México, DF (Mexico); Knobel, M. [Institute of Physics “Gleb Wataghin”, UNICAMP, 13083-970 Campinas, SP (Brazil); Reguera, E., E-mail: edilso.reguera@gmail.com [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México, DF (Mexico)

    2013-08-15

    This study sheds light on the intermolecular interactions between imidazole derive molecules (2-methyl-imidazole, 2-ethyl-imidazole and benzimidazole) intercalated in T[Ni(CN){sub 4}] layers to form a solid of formula unit T(ImD){sub 2}[Ni(CN){sub 4}]. These hybrid inorganic–organic solids were prepared by soft chemical routes and their crystal structures solved and refined from X-ray powder diffraction data. The involved imidazole derivative molecules were found coordinated through the pyridinic N atom to the axial positions for the metal T in the T[Ni(CN){sub 4}] layer. In the interlayers region ligand molecules from neighboring layers remain stacked in a face-to-face configuration through dipole–dipole and quadrupole–quadrupole interactions. These intermolecular interactions show a pronounced dependence on the substituent group and are responsible for an ImD-pillaring concatenation of adjacent layers. This is supported by the structural information and the recorded magnetic data in the 2–300 K temperature range. The samples containing Co and Ni are characterized by presence of spin–orbit coupling and pronounced temperature dependence for the effective magnetic moment except for 2-ethyl-imidazole related to the local distortion for the metal coordination environment. For this last one ligand a weak ferromagnetic ordering ascribed to a super-exchange interaction between T metals from neighboring layers through the ligands π–π interaction was detected. - Graphical abstract: In the interlayers region imidazole derivative molecules are oriented according to their dipolar and quadrupolar interactions and minimizing the steric impediment. Highlights: • Imidazole derivatives intercalation compounds. • Intermolecular interaction between intercalated imidazole derivatives. • Hybrid inorganic–organic solids. • Pi–pi interactions and ferromagnetic coupling. • Dipolar and quadrupolar interactions between intercalated imidazole derivatives.

  8. Study on Synthesis and Intercalation Behavior of Layered Zirconium Proline-N-methylphosphonate-phosphate

    Institute of Scientific and Technical Information of China (English)

    Xiao Ping RAO; Xiang Kai FU; Kai RAO

    2004-01-01

    Zirconium proline-N-methylphosphonate-phosphate (α-ZPMPP) was prepared in the presence of HF for the first time. The α-ZPMPP sample is highly crystallized with interlayer distance of 1.52 nm. The interlayer distance of complex of α-ZPMPP with n-butylamine (α-ZPMPP-BA) is in 0.45 nm larger than that of α-ZPMPP. The α-ZPMPP possesses different intercalation behavior of host-guest compound from α-ZP.

  9. Intercalation of methotrexatum into layered double hydroxides via exfoliation-reassembly process

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Su-Qing; Li, Shu-Ping, E-mail: lishuping@njnu.edu.cn; Li, Xiao-Dong, E-mail: lixiaodong1@njnu.edu.cn

    2015-03-01

    Graphical abstract: The intercalation of methotrexatum (MTX) into layered double hydroxides (LDHs) via an exfoliation-reassembly process was studied and the resulting MTX/LDHs hybrids were evaluated by anticancer effects on A549 cells together with pristine LDHs and MTX itself, the results indicated that the hybrids obtained from low concentration of MTX solution presented much better anticancer effect. - Highlights: • Exfoliation-reassembly process is a good method to synthesize hybrids. • MTX/LDHs from low concentration of MTX solution presented better release property. • MTX/LDHs from low concentration of MTX solution presented good anticancer effects. - Abstract: In this paper, the intercalation of methotrexatum (MTX) into layered double hydroxides (LDHs) via an exfoliation-reassembly process was reported and the resulting hybrids were then characterized by X-ray diffraction (XRD) patterns, Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM) patterns etc. In the synthesis procedure, LDHs particles were firstly delaminated into well-dispersed 2D nanosheets in formamide by ultrasonic treatment at room temperature, and then the resulting LDH nanosheets were reassembled in MTX solution to form MTX intercalated LDH (MTX/LDHs) hybrids. AFM images showed that during the exfoliation process a large part of LDHs particles were delaminated into single and double brucite layers. XRD patterns and FTIR investigations manifested the successful intercalation of MTX anions into LDHs interlayers for the final samples. It was also found out that the drug-loading capacity of the hybrids increased with the concentrations of MTX solutions, while the morphology became even aggregated. At last, the cell cytotoxicity of the hybrids was estimated by MTT assays on the human lung cancer cells (A549), and the results stated that MTX/LDHs hybrids had effective suppress role on the proliferation of cancer cells.

  10. Intercalation of benzoxaborolate anions in layered double hydroxides: toward hybrid formulations for benzoxaborole drugs

    OpenAIRE

    Sene, Saad; Bégu, Sylvie; Gervais, Christel; Renaudin, Guillaume; Mesbah, Adel; Smith, Mark,; Mutin, Hubert,; van der Lee, Arie; Nedelec, Jean-Marie; Bonhomme, Christian; Laurencin, Danielle

    2015-01-01

    International audience Benzoxaboroles are a family of cyclic derivatives of boronic acids, whose reactivity makes them interesting candidates for the development of novel drugs. In this study, we describe the preparation of the first hybrid organic-inorganic materials involving benzoxaboroles, as a first step towards their use as new formulations for such drugs. The materials were prepared by intercalation of the simplest benzoxaborole (C7H6BO(OH), BBzx) or of its fluorinated analogue (C7H...

  11. Bidirectional synaptic plasticity in intercalated amygdala neurons and the extinction of conditioned fear responses.

    Science.gov (United States)

    Royer, S; Paré, D

    2002-01-01

    Classical fear conditioning is believed to result from potentiation of conditioned synaptic inputs in the basolateral amygdala. That is, the conditioned stimulus would excite more neurons in the central nucleus and, via their projections to the brainstem and hypothalamus, evoke fear responses. However, much data suggests that extinction of fear responses does not depend on the reversal of these changes but on a parallel NMDA-dependent learning that competes with the first one. Because they control impulse traffic from the basolateral amygdala to the central nucleus, GABAergic neurons of the intercalated cell masses are ideally located to implement this second learning. Consistent with this hypothesis, the present study shows that low- and high-frequency stimulation of basolateral afferents respectively induce long-term depression (LTD) and potentiation (LTP) of responses in intercalated cells. Moreover, induction of LTP and LTD is prevented by application of an NMDA antagonist. To determine how these activity-dependent changes are expressed, we tested whether LTD and LTP induction are associated with modifications in paired-pulse facilitation, an index of transmitter release probability. Only LTP induction was associated with a change in paired-pulse facilitation. Depotentiation of previously potentiated synapses did not revert the modification in paired pulse facilitation, suggesting that LTP is associated with presynaptic alterations, but that LTD and depotentiation depend on postsynaptic changes. Taken together, our results suggest that basolateral synapses onto intercalated neurons can express NMDA-dependent LTP and LTD, consistent with the possibility that intercalated neurons are a critical locus of plasticity for the extinction of conditioned fear responses. Ultimately, these plastic events may prevent conditioned amygdala responses from exciting neurons of the central nucleus, and thus from evoking conditioned fear responses.

  12. Lithium Intercalation in Graphene/MoS2 Composites: First-Principles Insights

    CERN Document Server

    Shao, Xiji; Pang, Rui; Shi, Xingqiang

    2015-01-01

    As a storage material for Li-ion batteries, graphene/molybdenum disulfide (Gr/MoS2) composites have been intensively studied in experiments. But the relevant theoretical works from first-principles are lacking. In the current work, van-der-Waals-corrected density functional theory calculations are performed to investigate the interaction of Li in Gr/MoS2 composites. Three interesting features are revealed for the intercalated Gr/Li(n)/MoS2 composites (n = 1 to 9). One is the reason for large Li storage capacity of Gr/MoS2: due to the binding energies per Li atom increase with the increasing number of intercalated Li atoms. Secondly, the band gap opening of Gr is found, and the band gap is enlarged with the increasing number of intercalated Li atoms, up to 160 meV with nine Li; hence these results suggest an efficient way to tune the band gap of graphene. Thirdly, the Dirac cone of Gr always preserve for different number of ionic bonded Li atoms.

  13. 1MAS NMR spectra of kao linite/formamide intercalation compound

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The high spinning speed 1H magic angle spinning nuclear magnetic resonance (1H MAS NMR) technique was employed to distinguish the two groups of surface hydroxyls of kaolinite and investigate the intercalation mechanism of kaolinite/formamide compound. The proton chemical shifts of the inner hydroxyl and inner surface hydroxyl of kaolinte are in the range of δ-1.3-0.9 and δ 2.4-3.0 respectively. After formamide intercalation three proton peaks were detected. The proton peak of the inner surface hydroxyls of the intercalation compound shifts to high-field with δ 2.3-2.7, which is assigned to the formation of the hydrogen bond between the inner surface hydroxyl and formamide carbonyl group. Whereas, the proton peak of the inner hydroxyl shifts to δ-0.3 toward low-field, that is attributed to van der Waal's effect between the inner hydroxyl proton and the amino group proton of the formamide which may be keyed into the ditrigonal hole of the kaolinite. The third peak, additional proton peak, is in the range of δ5.4-5.6, that is ascribed to the hydrogen bond formation between the amino group proton of formimide and SiO4 tetrahedral oxygen of the kaolinite.

  14. Effects of Intercalation on the Hole Mobility of Amorphous Semiconducting Polymer Blends

    KAUST Repository

    Cates, Nichole C.

    2010-06-08

    Fullerenes have been shown to intercalate between the side chains of many crystalline and semicrystalline polymers and to affect the properties of polymer:fullerene bulk heterojunction solar cells. Here we present the first in-depth study of intercalation in an amorphous polymer. We study blends of the widely studied amorphous polymer poly(2-methoxy-5-(3studied amorphous polymer poly(,7·studied amorphous polymer poly(-dimethyloctyloxy)-p-phenylene vinylene) (MDMO-PPV) with a variety of molecules using photoluminescence measurements, scanning electron microscopy, and space-charge limited current mobility measurements. The blends with elevated hole mobilities exhibit complete photoluminescence quenching and show no phase separation in a scanning electron microscope. We conclude that intercalation occurs in MDMO-PPV:fullerene blends and is responsible for the increase in the MDMO-PPV hole mobility by several orders of magnitude when it is blended with fullerenes, despite the dilution of the hole-conducting polymer with an electron acceptor. © 2010 American Chemical Society.

  15. Intercalation of amino acids and oligopeptides into Zn Al layered double hydroxide by coprecipitation reaction

    Science.gov (United States)

    Aisawa, Sumio; Sasaki, Shuji; Takahashi, Satoshi; Hirahara, Hidetoshi; Nakayama, Hirokazu; Narita, Eiichi

    2006-05-01

    The coprecipitation of amino acids and oligopeptides with the Zn Al LDH was investigated using phenylalanine (Phe), phenylalanyl-phenylalanine (Phe-Phe), glycyl-phenylalanine (Gly Phe), glycine (Gly), glycyl-glycine (Gly Gly), glycyl-glycyl-glycine (Gly Gly Gly) and N-(N-γ-glutamyl-cysteinyl)-glycine (GSH) as guest species. The coprecipitation behavior of amino acids and oligopeptides was found to be influenced by the solution pH and the kind of their side chain groups, and reached the maximum at pH 8 or 9. The basal spacing, d003, of the Phe, Phe-Phe and GSH/LDH was 1.81, 2.41 and 1.64 nm, supporting that guests were arranged vertical to the LDH basal layer. Acceding to the basal spacing of the Gly, Gly Gly and Gly Gly Gly/LDH (d003=0.84 0.88 nm), these guests were oriented horizontal to the LDH basal layer with the co-intercalated NO3-. Moreover, the amount of Phe-Phe, Gly Gly and Gly Gly Gly intercalated was almost the same as that of Phe and Gly despite increasing the number peptide bond and the molecular size. GSH was intercalated into the LDH interlayer space as GSH oxidized form with bridged LDH layers by their carboxylate groups.

  16. Hydrogen storage in Li-doped fullerene-intercalated hexagonal boron nitrogen layers

    Science.gov (United States)

    Cheng, Yi-Han; Zhang, Chuan-Yu; Ren, Juan; Tong, Kai-Yu

    2016-10-01

    New materials for hydrogen storage of Li-doped fullerene (C20, C28, C36, C50, C60, C70)-intercalated hexagonal boron nitrogen ( h-BN) frameworks were designed by using density functional theory (DFT) calculations. First-principles molecular dynamics (MD) simulations showed that the structures of the C n -BN ( n = 20, 28, 36, 50, 60, and 70) frameworks were stable at room temperature. The interlayer distance of the h-BN layers was expanded to 9.96-13.59 Å by the intercalated fullerenes. The hydrogen storage capacities of these three-dimensional (3D) frameworks were studied using grand canonical Monte Carlo (GCMC) simulations. The GCMC results revealed that at 77 K and 100 bar (10 MPa), the C50-BN framework exhibited the highest gravimetric hydrogen uptake of 6.86 wt% and volumetric hydrogen uptake of 58.01 g/L. Thus, the hydrogen uptake of the Li-doped C n -intercalated h-BN frameworks was nearly double that of the non-doped framework at room temperature. Furthermore, the isosteric heats of adsorption were in the range of 10-21 kJ/mol, values that are suitable for adsorbing/desorbing the hydrogen molecules at room temperature. At 193 K (-80 °C) and 100 bar for the Li-doped C50-BN framework, the gravimetric and volumetric uptakes of H2 reached 3.72 wt% and 30.08 g/L, respectively.

  17. A naproxen complex of dysprosium intercalates into calf thymus DNA base pairs

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Mengsi; Jin, Jianhua; Xu, Guiqing [School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Xinxiang 453007 (China); Cui, Fengling, E-mail: fenglingcui@hotmail.com [School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Xinxiang 453007 (China); Luo, Hongxia [Department of Chemistry, Renmin University of China, Beijing 100872 (China)

    2014-01-15

    Highlights: • Binding mode to ctDNA was studied by various methods. • Intercalation is the most possible binding mode. • Dynamic and static quenching occurred simultaneously. • Hydrophobic force played a major role. • Binding characteristic of rare earth complexes to DNA are dependent on the element. - Abstract: The binding mode and mechanism of dysprosium–naproxen complex (Dy–NAP) with calf thymus deoxyribonucleic acid (ctDNA) were studied using UV–vis and fluorescence spectra in physiological buffer (pH 7.4). The results showed that more than one type of quenching process occurred and the binding mode between Dy–NAP with ctDNA might be intercalation. In addition, ionic strength, iodide quenching and fluorescence polarization experiments corroborated the intercalation binding mode between Dy–NAP and ctDNA. The calculated thermodynamic parameters ΔG, ΔH and ΔS at different temperature demonstrated that hydrophobic interaction force played a major role in the binding process.

  18. X-ray absorption studies of graphite intercalates and metal-ammonia solutions

    International Nuclear Information System (INIS)

    X-ray absorption spectroscopy (XAS) was used to study the arsenic fluorocomplexes, including the AsF5 and AsF6- intercalates of graphite, and rubidium metal-ammonia solutions. The As-F distances obtained for AsF3 and AsF5 gas are both in excellent agreement with electron diffraction data (within 0.004 A). A superior measurement which is significantly shorter than the accepted value of the bond distance in an undistorted AsF6- octahedra is reported. Both the XAES and EXAFS data presented support the hypothesis that the AsF5 oxidizes graphite upon intercalation to produce AsF6- and AsF3 intercalant species. Changes in the Rb K-edge features which are consistent with the known properties of Rb-NH3 are correlated with conductivity and delocalization of the solvated electrons. In the XAES region, intensity and position changes of absorption transitions are explained. In the EXAFS region, the Rb-N bond distance and the relative number of nitrogen atoms in the first shell are measured. XAS has been shown to provide unique information about the nature of the metal-ammonia phase separation, phase transition, and density fluctuations

  19. Intercalation of methotrexatum into layered double hydroxides via exfoliation-reassembly process

    Science.gov (United States)

    Liu, Su-Qing; Li, Shu-Ping; Li, Xiao-Dong

    2015-03-01

    In this paper, the intercalation of methotrexatum (MTX) into layered double hydroxides (LDHs) via an exfoliation-reassembly process was reported and the resulting hybrids were then characterized by X-ray diffraction (XRD) patterns, Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM) patterns etc. In the synthesis procedure, LDHs particles were firstly delaminated into well-dispersed 2D nanosheets in formamide by ultrasonic treatment at room temperature, and then the resulting LDH nanosheets were reassembled in MTX solution to form MTX intercalated LDH (MTX/LDHs) hybrids. AFM images showed that during the exfoliation process a large part of LDHs particles were delaminated into single and double brucite layers. XRD patterns and FTIR investigations manifested the successful intercalation of MTX anions into LDHs interlayers for the final samples. It was also found out that the drug-loading capacity of the hybrids increased with the concentrations of MTX solutions, while the morphology became even aggregated. At last, the cell cytotoxicity of the hybrids was estimated by MTT assays on the human lung cancer cells (A549), and the results stated that MTX/LDHs hybrids had effective suppress role on the proliferation of cancer cells.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Haifeng; Tang, Pinggui [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Feng, Yongjun, E-mail: yjfeng@mail.buct.edu.cn [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Wang, Lijing; Li, Dianqing [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

    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.