Li intercalation in graphite: A van der Waals density-functional study

NASA Astrophysics Data System (ADS)

Hazrati, E.; de Wijs, G. A.; Brocks, G.

2014-10-01

Modeling layered intercalation compounds from first principles poses a problem, as many of their properties are determined by a subtle balance between van der Waals interactions and chemical or Madelung terms, and a good description of van der Waals interactions is often lacking. Using van der Waals density functionals we study the structures, phonons and energetics of the archetype layered intercalation compound Li-graphite. Intercalation of Li in graphite leads to stable systems with calculated intercalation energies of -0.2 to -0.3 eV/Li atom, (referred to bulk graphite and Li metal). The fully loaded stage 1 and stage 2 compounds LiC6 and Li1 /2C6 are stable, corresponding to two-dimensional √{3 }×√{3 } lattices of Li atoms intercalated between two graphene planes. Stage N >2 structures are unstable compared to dilute stage 2 compounds with the same concentration. At elevated temperatures dilute stage 2 compounds easily become disordered, but the structure of Li3 /16C6 is relatively stable, corresponding to a √{7 }×√{7 } in-plane packing of Li atoms. First-principles calculations, along with a Bethe-Peierls model of finite temperature effects, allow for a microscopic description of the observed voltage profiles.

Plant Flavone Apigenin Binds to Nucleic Acid Bases and Reduces Oxidative DNA Damage in Prostate Epithelial Cells

PubMed Central

Bhaskaran, Natarajan; Gupta, Sanjay

2014-01-01

Oxidative stress has been linked to prostate carcinogenesis as human prostate tissue is vulnerable to oxidative DNA damage. Apigenin, a dietary plant flavone, possesses anti-proliferative and anticancer effects; however, its antioxidant properties have not been fully elucidated. We investigated sub-cellular distribution of apigenin, it’s binding to DNA and protective effects against H2O2-induced DNA damage using transformed human prostate epithelial RWPE-1 cells and prostate cancer LNCaP, PC-3 and DU145 cells. Exposure of cells to apigenin exhibited higher accumulation in RWPE-1 and LNCaP cells, compared to PC-3 and DU145 cells. The kinetics of apigenin uptake in LNCaP cells was estimated with a Km value of 5 µmole/L and Vmax of 190 pmoles/million cells/h. Sub-cellular fractionation demonstrated that nuclear matrix retains the highest concentration of apigenin (45.3%), followed by cytosol (23.9%), nuclear membranes (17.9%) and microsomes (12.9%), respectively. Spectroscopic analysis of apigenin with calf-thymus DNA exhibited intercalation as the dominant binding mode to DNA duplex. Apigenin exposure resulted in significant genoprotective effects in H2O2-stressed RWPE-1 cells by reduction in reactive oxygen species levels. In addition, apigenin exposure suppressed the formation of 8-hydroxy-2′ deoxyguanosine and protected exposed cells from apoptosis. Our studies demonstrate that apigenin is readily taken up by normal prostatic epithelial cells and prostate cancer cells, and is incorporated into their nuclei, where its intercalation with nucleic acid bases may account for its antioxidant and chemopreventive activities. PMID:24614817

Plant flavone apigenin binds to nucleic acid bases and reduces oxidative DNA damage in prostate epithelial cells.

PubMed

Sharma, Haripaul; Kanwal, Rajnee; Bhaskaran, Natarajan; Gupta, Sanjay

2014-01-01

Oxidative stress has been linked to prostate carcinogenesis as human prostate tissue is vulnerable to oxidative DNA damage. Apigenin, a dietary plant flavone, possesses anti-proliferative and anticancer effects; however, its antioxidant properties have not been fully elucidated. We investigated sub-cellular distribution of apigenin, it's binding to DNA and protective effects against H2O2-induced DNA damage using transformed human prostate epithelial RWPE-1 cells and prostate cancer LNCaP, PC-3 and DU145 cells. Exposure of cells to apigenin exhibited higher accumulation in RWPE-1 and LNCaP cells, compared to PC-3 and DU145 cells. The kinetics of apigenin uptake in LNCaP cells was estimated with a Km value of 5 µmole/L and Vmax of 190 pmoles/million cells/h. Sub-cellular fractionation demonstrated that nuclear matrix retains the highest concentration of apigenin (45.3%), followed by cytosol (23.9%), nuclear membranes (17.9%) and microsomes (12.9%), respectively. Spectroscopic analysis of apigenin with calf-thymus DNA exhibited intercalation as the dominant binding mode to DNA duplex. Apigenin exposure resulted in significant genoprotective effects in H2O2-stressed RWPE-1 cells by reduction in reactive oxygen species levels. In addition, apigenin exposure suppressed the formation of 8-hydroxy-2' deoxyguanosine and protected exposed cells from apoptosis. Our studies demonstrate that apigenin is readily taken up by normal prostatic epithelial cells and prostate cancer cells, and is incorporated into their nuclei, where its intercalation with nucleic acid bases may account for its antioxidant and chemopreventive activities.

Preparation of graphite intercalation compounds containing oligo and polyethers

NASA Astrophysics Data System (ADS)

Zhang, Hanyang; Lerner, Michael M.

2016-02-01

Layered host-polymer nanocomposites comprising polymeric guests between inorganic sheets have been prepared with many inorganic hosts, but there is limited evidence for the incorporation of polymeric guests into graphite. Here we report for the first time the preparation, and structural and compositional characterization of graphite intercalation compounds (GICs) containing polyether bilayers. The new GICs are obtained by either (1) reductive intercalation of graphite with an alkali metal in the presence of an oligo or polyether and an electrocatalyst, or (2) co-intercalate exchange of an amine for an oligo or polyether in a donor-type GIC. Structural characterization of products using powder X-ray diffraction, Raman spectroscopy, and thermal analyses supports the formation of well-ordered, first-stage GICs containing alkali metal cations and oligo or polyether bilayers between reduced graphene sheets.Layered host-polymer nanocomposites comprising polymeric guests between inorganic sheets have been prepared with many inorganic hosts, but there is limited evidence for the incorporation of polymeric guests into graphite. Here we report for the first time the preparation, and structural and compositional characterization of graphite intercalation compounds (GICs) containing polyether bilayers. The new GICs are obtained by either (1) reductive intercalation of graphite with an alkali metal in the presence of an oligo or polyether and an electrocatalyst, or (2) co-intercalate exchange of an amine for an oligo or polyether in a donor-type GIC. Structural characterization of products using powder X-ray diffraction, Raman spectroscopy, and thermal analyses supports the formation of well-ordered, first-stage GICs containing alkali metal cations and oligo or polyether bilayers between reduced graphene sheets. Electronic supplementary information (ESI) available: Domain size, additional Raman spectra info, compositional calculation, and packing fractions. See DOI: 10.1039/c5nr08226a

Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yi, Tanghong; Chen, Wei; Cheng, Lei

Reversible intercalation reactions provide the basis for modern battery electrodes. In spite of the decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K+ ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopymore » confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. Our study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less

Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yi, Tanghong; Chen, Wei; Cheng, Lei

Reversible intercalation reactions provide the basis for modern battery electrodes. Despite decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K + ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed themore » existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. This study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less

Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

DOE PAGES

Yi, Tanghong; Chen, Wei; Cheng, Lei; ...

2017-01-20

Reversible intercalation reactions provide the basis for modern battery electrodes. In spite of the decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K+ ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopymore » confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. Our study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less

Effect of metal ion intercalation on the structure of MXene and water dynamics on its internal surfaces

DOE PAGES

Osti, Naresh C.; Naguib, Michael; Ostadhossein, Alireza; ...

2016-03-24

MXenes are a recently discovered class of 2D materials with an excellent potential for energy storage applications. Because MXene surfaces are hydrophilic and attractive interaction forces between the layers are relatively weak, water molecules can spontaneously intercalate at ambient humidity and significantly influence the key properties of this 2D material. Using complementary X-ray and neutron scattering techniques, we demonstrate that intercalation with potassium cations significantly improves structural homogeneity and water stability in MXenes. Furthermore, in agreement with molecular dynamics simulations, intercalated potassium ions reduce the water self-diffusion coefficient by 2 orders of magnitude, suggesting greater stability of hydrated MXene againstmore » changing environmental conditions.« less

Carbon Nanotube Anodes Being Evaluated for Lithium Ion Batteries

NASA Technical Reports Server (NTRS)

Raffaelle, Ryne P.; Gennett, Tom; VanderWal, Randy L.; Hepp, Aloysius F.

2001-01-01

The NASA Glenn Research Center is evaluating the use of carbon nanotubes as anode materials for thin-film lithium-ion (Li) batteries. The motivation for this work lies in the fact that, in contrast to carbon black, directed structured nanotubes and nanofibers offer a superior intercalation media for Li-ion batteries. Carbon lamellas in carbon blacks are circumferentially oriented and block much of the particle interior, rendering much of the matrix useless as intercalation material. Nanofibers, on the other hand, can be grown so as to provide 100-percent accessibility of the entire carbon structure to intercalation. These tubes can be visualized as "rolled-up" sheets of carbon hexagons (see the following figure). One tube is approximately 1/10,000th the diameter of a human hair. In addition, the high accessibility of the structure confers a high mobility to ion-exchange processes, a fundamental for the batteries to respond dynamically because of intercalation.

Comparison of fluoride intercalation/de-intercalation processes on graphite electrodes in aqueous and aqueous methanolic HF media

NASA Astrophysics Data System (ADS)

Noel, M.; Santhanam, R.; Francisca Flora, M.

The solvent can play a major role in the intercalation/de-intercalation process and the stability of graphite substrates towards this process. This fact is established in the present work that involves fluoride intercalation/de-intercatlation on graphite electrodes in aqueous and aqueous methanolic HF solutions where the HF concentration is varied between 1.0 and 18.0 M. In addition to cyclic voltammetry and potentiostatic polarization, open-circuit potential decay measurements, scanning electron microscopy and X-ray diffraction measurements have been employed. In general, addition of methanol and increasing concentration of HF raise the overall intercalation/de-intercalation efficiency. Methanol is adsorbed preferentially on the graphite lattice and, hence, suppresses both oxygen evolution and the formation of passive graphite oxides. In 15.0 M HF, the optimum methanol concentration is 5 vol.%. This suggests that, in addition to the adsorption effect, there is some weakening of the structured water molecules that facilitates the solvated fluoride ions for efficient intercalation.

Superconducting selenides intercalated with organic molecules: synthesis, crystal structure, electric and magnetic properties, superconducting properties, and phase separation in iron based-chalcogenides and hybrid organic-inorganic superconductors

NASA Astrophysics Data System (ADS)

Krzton-Maziopa, Anna; Pesko, Edyta; Puzniak, Roman

2018-06-01

Layered iron-based superconducting chalcogenides intercalated with molecular species are the subject of intensive studies, especially in the field of solid state chemistry and condensed matter physics, because of their intriguing chemistry and tunable electric and magnetic properties. Considerable progress in the research, revealing superconducting inorganic–organic hybrid materials with transition temperatures to superconducting state, T c, up to 46 K, has been brought in recent years. These novel materials are synthesized by low-temperature intercalation of molecular species, such as solvates of alkali metals and nitrogen-containing donor compounds, into layered FeSe-type structure. Both the chemical nature as well as orientation of organic molecules between the layers of inorganic host, play an important role in structural modifications and may be used for fine tuning of superconducting properties. Furthermore, a variety of donor species compatible with alkali metals, as well as the possibility of doping also in the host structure (either on Fe or Se sites), makes this system quite flexible and gives a vast array of new materials with tunable electric and magnetic properties. In this review, the main aspects of intercalation chemistry are discussed with a particular attention paid to the influence of the unique nature of intercalating species on the crystal structure and physical properties of the hybrid inorganic–organic materials. To get a full picture of these materials, a comprehensive description of the most effective chemical and electrochemical methods, utilized for synthesis of intercalated species, with critical evaluation of their strong and weak points, related to feasibility of synthesis, phase purity, crystal size and morphology of final products, is included as well.

Calcium intercalation into layered fluorinated sodium iron phosphate

NASA Astrophysics Data System (ADS)

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei; Liao, Chen; Fister, Timothy T.; Ingram, Brian J.

2017-11-01

The energy density and cost of battery systems, relative to the current state-of-the art, can be improved by developing alternative chemistries utilizing multivalent working ions such as calcium. Many challenges must be overcome, such as the identification of cathode materials with high energy density and an electrolyte with a wide electrochemical stability window that can plate and strip calcium metal, before market implementation. Herein, the feasibility and cycling performance of Ca2+ intercalation into a desodiated layered Na2FePO4F host is described. This is the first demonstration of Ca2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca2+ intercalation. Although substantial effort is expected in order to develop a high energy density cathode material, this study demonstrates the feasibility of Ca2+ intercalation into multiple host structures types, thereby extending opportunities for development of Ca insertion host structures, suggesting such a cathode material can be identified and developed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osiry, H.; Cano, A.; Lemus-Santana, A.A.

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 wasmore » 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.« less

Stability of Ruddlesden–Popper-structured oxides in humid conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lehtimäki, M.; Yamauchi, H.; Karppinen, M., E-mail: maarit.karppinen@aalto.fi

2013-08-15

Some of layered transition-metal oxides are known to react with atmospheric humidity to form through topotactic intercalation reactions new water-containing layered structures. Here we investigate the influence of oxygen content (7−δ) of the Ruddlesden–Popper-structured Sr{sub 3}FeMO{sub 7−δ} (M=Ni, Mn, Ti) oxides on the water-intercalation reaction. It is found that their oxygen contents influence greatly the reactivity of the phases with water. Other factors possibly affecting the reactivity are discussed on the basis of the present data in combination with a comprehensive review of previous works on Ruddlesden–Popper and related layered oxide phases. - Graphical abstract: Many of the Ruddlesden–Popper-structured A{submore » 3}B{sub 2}O{sub 7−δ} oxides readily react with water via intercalation reactions. Three possible factors affecting the water intercalation are identified: oxygen content of the phase, ionic radius of cation A and valence state of cation B. The resultant layered water-derivative phases can be categorised into two groups, depending on the crystal symmetry of the phase. Highlights: • Ruddlesden–Popper oxides A{sub 3}B{sub 2}O{sub 7−δ} often accommodate water via intercalation reaction. • The lower the oxygen content 7−δ is the more readily the intercalation reaction occurs. • The second factor promoting the reaction is the large size of cation A. • The third possible factor is the high valence state of cation B. • Resultant water-derivatives can be categorised into two groups depending on symmetry.« less

Process for producing advanced ceramics

DOEpatents

Kwong, Kyei-Sing

1996-01-01

A process for the synthesis of homogeneous advanced ceramics such as SiC+AlN, SiAlON, SiC+Al.sub.2 O.sub.3, and Si.sub.3 N.sub.4 +AlN from natural clays such as kaolin, halloysite and montmorillonite by an intercalation and heat treatment method. Included are the steps of refining clays, intercalating organic compounds into the layered structure of clays, drying the intercalated mixture, firing the treated atmospheres and grinding the loosely agglomerated structure. Advanced ceramics produced by this procedure have the advantages of homogeneity, cost effectiveness, simplicity of manufacture, ease of grind and a short process time. Advanced ceramics produced by this process can be used for refractory, wear part and structure ceramics.

Nano-scaled top-down of bismuth chalcogenides based on electrochemical lithium intercalation

NASA Astrophysics Data System (ADS)

Chen, Jikun; Zhu, Yingjie; Chen, Nuofu; Liu, Xinling; Sun, Zhengliang; Huang, Zhenghong; Kang, Feiyu; Gao, Qiuming; Jiang, Jun; Chen, Lidong

2011-12-01

A two-step method has been used to fabricate nano-particles of layer-structured bismuth chalcogenide compounds, including Bi2Te3, Bi2Se3, and Bi2Se0.3Te2.7, through a nano-scaled top-down route. In the first step, lithium (Li) atoms are intercalated between the van der Waals bonded quintuple layers of bismuth chalcogenide compounds by controllable electrochemical process inside self-designed lithium ion batteries. And in the second step, the Li intercalated bismuth chalcogenides are subsequently exposed to ethanol, in which process the intercalated Li atoms would explode like atom-scaled bombs to exfoliate original microscaled powder into nano-scaled particles with size around 10 nm. The influence of lithium intercalation speed and amount to three types of bismuth chalcogenide compounds are compared and the optimized intercalation conditions are explored. As to maintain the phase purity of the final nano-particle product, the intercalation lithium amount should be well controlled in Se contained bismuth chalcogenide compounds. Besides, compared with binary bismuth chalcogenide compound, lower lithium intercalation speed should be applied in ternary bismuth chalcogenide compound.

Hydrogenation and hydrogen intercalation of hexagonal boron nitride on Ni(1 1 1): reactivity and electronic structure

NASA Astrophysics Data System (ADS)

Späth, F.; Gebhardt, J.; Düll, F.; Bauer, U.; Bachmann, P.; Gleichweit, C.; Görling, A.; Steinrück, H.-P.; Papp, C.

2017-09-01

We investigate the reactivity of hexagonal boron nitride (h-BN) on a Ni(1 1 1) single crystal towards atomic hydrogen over a wide exposure range. Near edge x-ray absorption fine structure and x-ray photoelectron spectroscopy (XPS) show that for low hydrogen exposures hydrogenation of the h-BN sheet is found. In contrast, intercalation of hydrogen between h-BN and the Ni(1 1 1) substrate occurs for high exposures. For intermediate regimes, a mixture of intercalation and hydrogenation is observed. From temperature-programmed desorption and temperature-programmed XPS experiments, we conclude that the hydrogen covalently bound to h-BN is rather stable with a desorption temperature of 600 K, while intercalated hydrogen is desorbing already at 390 K. Further insight into the structural arrangements and the thermodynamics of the system is obtained by comparing our experimental results with extensive density-functional theory calculations. Together with ultraviolet photoelectron spectroscopy measurements, the calculations provide detailed insight into the influence of hydrogenation on the electronic structure of h-BN.

The effect of hydrazine intercalation on the structure and capacitance of 2D titanium carbide (MXene)

DOE PAGES

Mashtalir, O.; Lukatskaya, Maria R.; Kolesnikov, Alexander I.; ...

2016-03-25

Herein we show that hydrazine intercalation into 2D titanium carbide (Ti 3C 2-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 Ti 3C 2T x layers pre-opening the structure and improving the accessability to active sites. Furthermore, 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.

X-ray Spectroscopy and Imaging as Multiscale Probes of Intercalation Phenomena in Cathode Materials

NASA Astrophysics Data System (ADS)

Horrocks, Gregory A.; De Jesus, Luis R.; Andrews, Justin L.; Banerjee, Sarbajit

2017-09-01

Intercalation phenomena are at the heart of modern electrochemical energy storage. Nevertheless, as out-of-equilibrium processes involving concomitant mass and charge transport, such phenomena can be difficult to engineer in a predictive manner. The rational design of electrode architectures requires mechanistic understanding of physical phenomena spanning multiple length scales, from atomistic distortions and electron localization at individual transition metal centers to phase inhomogeneities and intercalation gradients in individual particles and concentration variances across ensembles of particles. In this review article, we discuss the importance of the electronic structure in mediating electrochemical storage and mesoscale heterogeneity. In particular, we discuss x-ray spectroscopy and imaging probes of electronic and atomistic structure as well as statistical regression methods that allow for monitoring of the evolution of the electronic structure as a function of intercalation. The layered α-phase of V2O5 is used as a model system to develop fundamental ideas on the origins of mesoscale heterogeneity.

Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids

NASA Astrophysics Data System (ADS)

Romero, F. Denis; Pitcher, M. J.; Hiley, C. I.; Whitehead, G. F. S.; Kar, S.; Ganin, A. Y.; Antypov, D.; Collins, C.; Dyer, M. S.; Klupp, G.; Colman, R. H.; Prassides, K.; Rosseinsky, M. J.

2017-07-01

Alkali metal intercalation into polyaromatic hydrocarbons (PAHs) has been studied intensely after reports of superconductivity in a number of potassium- and rubidium-intercalated materials. There are, however, no reported crystal structures to inform our understanding of the chemistry and physics because of the complex reactivity of PAHs with strong reducing agents at high temperature. Here we present the synthesis of crystalline K2Pentacene and K2Picene by a solid-solid insertion protocol that uses potassium hydride as a redox-controlled reducing agent to access the PAH dianions, and so enables the determination of their crystal structures. In both cases, the inserted cations expand the parent herringbone packings by reorienting the molecular anions to create multiple potassium sites within initially dense molecular layers, and thus interact with the PAH anion π systems. The synthetic and crystal chemistry of alkali metal intercalation into PAHs differs from that into fullerenes and graphite, in which the cation sites are pre-defined by the host structure.

Effect of molecular intercalation on the local structure of superconducting Nax(NH3)yMoSe2 system

NASA Astrophysics Data System (ADS)

Simonelli, L.; Paris, E.; Wakita, T.; Marini, C.; Terashima, K.; Miao, X.; Olszewski, W.; Ramanan, N.; Heinis, D.; Kubozono, Y.; Yokoya, T.; Saini, N. L.

2017-12-01

We have studied the local structure of layered Nax(NH3)yMoSe2 system by Mo K-edge extended X-ray absorption fine structure (EXAFS) measurements performed as a function of temperature. We find that molecular intercalation in MoSe2 largely affects the Mo-Se network while Mo-Mo seems to sustain small changes. The Einstein temperature (ΘE) of Mo-Mo distance hardly changes (∼264 K) indicating that bond strength of this distance remains unaffected by intercalation. On the other hand, Mo-Se distance suffers a softening, revealed by the decrease of ΘE from ∼364 K to ∼350 K. The results indicate that Na+ ion transported by NH3 molecules may enter between the two MoSe-layers resulting reduced Se-Se coupling. Therefore, increased hybridization between Se 4p and Mo 4d orbitals due to inter-layer disorder is the likely reason of metallicity in intercalated MoSe2 and superconductivity at low temperature.

Intercalated graphite fiber composites as EMI shields in aerospace structures

NASA Technical Reports Server (NTRS)

Gaier, James R.

1990-01-01

The requirements for electromagnetic interference (EMI) shielding in aerospace structures are complicated over that of ground structures by their weight limitations. As a result, the best EMI shielding materials must blend low density, high strength, and high elastic modulus with high shielding ability. In addition, fabrication considerations including penetrations and joints play a major role. The EMI shielding properties are calculated for shields formed from pristine and intercalated graphite fiber/epoxy composites and compared to preliminary experimental results and to shields made from aluminum. Calculations indicate that 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 properties alone.

Intercalation and structural aspects of macroRAFT agents into MgAl layered double hydroxides.

PubMed

Kostadinova, Dessislava; Cenacchi Pereira, Ana; Lansalot, Muriel; D'Agosto, Franck; Bourgeat-Lami, Elodie; Leroux, Fabrice; Taviot-Guého, Christine; Cadars, Sylvian; Prevot, Vanessa

2016-01-01

Increasing attention has been devoted to the design of layered double hydroxide (LDH)-based hybrid materials. In this work, we demonstrate the intercalation by anion exchange process of poly(acrylic acid) (PAA) and three different hydrophilic random copolymers of acrylic acid (AA) and n -butyl acrylate (BA) with molar masses ranging from 2000 to 4200 g mol -1 synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, into LDH containing magnesium(II) and aluminium(III) intralayer cations and nitrates as counterions (MgAl-NO 3 LDH). At basic pH, the copolymer chains (macroRAFT agents) carry negative charges which allowed the establishment of electrostatic interactions with the LDH interlayer and their intercalation. The resulting hybrid macroRAFT/LDH materials displayed an expanded interlamellar domain compared to pristine MgAl-NO 3 LDH from 1.36 nm to 2.33 nm. Depending on the nature of the units involved into the macroRAFT copolymer (only AA or AA and BA), the intercalation led to monolayer or bilayer arrangements within the interlayer space. The macroRAFT intercalation and the molecular structure of the hybrid phases were further characterized by Fourier transform infrared (FTIR) and solid-state 13 C, 1 H and 27 Al nuclear magnetic resonance (NMR) spectroscopies to get a better description of the local structure.

Exfoliation of Hexagonal Boron Nitride via Ferric Chloride Intercalation

NASA Technical Reports Server (NTRS)

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.

From nicotinate-containing layered double hydroxides (LDHs) to NAD coenzyme-LDH nanocomposites - Syntheses and structural characterization by various spectroscopic methods

NASA Astrophysics Data System (ADS)

Muráth, Szabolcs; Dudás, Csilla; Kukovecz, Ákos; Kónya, Zoltán; Sipos, Pál; Pálinkó, István

2017-07-01

The syntheses of nicotinate anion- and NAD coenzyme-layered double hydroxide (LDH) composites were performed with the aim of having the organic component among the layers. In-house prepared CaAl-LDHs were the host materials. Intercalation was attempted by direct ion exchange or by the dehydration-rehydration method applying aqueous solvent mixtures (containing ethanol, propanol, acetone, N,N-dimethylformamide). For structural characterization, beside X-ray diffractometry, X-ray photoelectron and IR spectroscopies, transmission and scanning electron microscopies as well as energy-dispersive X-ray analysis were used. Molecular modelling served for the visualization of the arrangements of the intercalated ions among the layers of the LDH samples. Although not all the intercalation methods and solvent mixtures led to intercalated composite materials, successful ones could be identified. The combination of spectroscopic methods helped in proposing sensible spatial arrangements for the intercalated anions. The NAD-CaAl-LDH composite proved to be an active catalyst in the oxidation of hydroquinone to 1,4-bezoquinoe in the presence of H2O2.

Mechanisms of small molecule–DNA interactions probed by single-molecule force spectroscopy

PubMed Central

Almaqwashi, Ali A.; Paramanathan, Thayaparan; Rouzina, Ioulia; Williams, Mark C.

2016-01-01

There is a wide range of applications for non-covalent DNA binding ligands, and optimization of such interactions requires detailed understanding of the binding mechanisms. One important class of these ligands is that of intercalators, which bind DNA by inserting aromatic moieties between adjacent DNA base pairs. Characterizing the dynamic and equilibrium aspects of DNA-intercalator complex assembly may allow optimization of DNA binding for specific functions. Single-molecule force spectroscopy studies have recently revealed new details about the molecular mechanisms governing DNA intercalation. These studies can provide the binding kinetics and affinity as well as determining the magnitude of the double helix structural deformations during the dynamic assembly of DNA–ligand complexes. These results may in turn guide the rational design of intercalators synthesized for DNA-targeted drugs, optical probes, or integrated biological self-assembly processes. Herein, we survey the progress in experimental methods as well as the corresponding analysis framework for understanding single molecule DNA binding mechanisms. We discuss briefly minor and major groove binding ligands, and then focus on intercalators, which have been probed extensively with these methods. Conventional mono-intercalators and bis-intercalators are discussed, followed by unconventional DNA intercalation. We then consider the prospects for using these methods in optimizing conventional and unconventional DNA-intercalating small molecules. PMID:27085806

Electronic structure of the chiral helimagnet and 3d-intercalated transition metal dichalcogenide Cr 1/3NbS 2

DOE PAGES

Sirca, N.; Mo, S. -K.; Bondino, F.; ...

2016-08-18

The electronic structure of the chiral helimagnet Cr 1/3NbS 2 has been studied with core level and angle-resolved photoemission spectroscopy (ARPES). Intercalated Cr atoms are found to be effective in donating electrons to the NbS 2 layers but also cause significant modifications of the electronic structure of the host NbS 2 material. Specifically, the data provide evidence that a description of the electronic structure of Cr 1/3NbS 2 on the basis of a simple rigid band picture is untenable. The data also reveal substantial inconsistencies with the predictions of standard density functional theory. In conclusion, the relevance of these resultsmore » to the attainment of a correct description of the electronic structure of chiral helimagnets, magnetic thin films/multilayers, and transition metal dichalcogenides intercalated with 3d magnetic elements is discussed.« less

Discriminating Intercalative Effects of Threading Intercalator Nogalamycin, from Classical Intercalator Daunomycin, Using Single Molecule Atomic Force Spectroscopy.

PubMed

Banerjee, T; Banerjee, S; Sett, S; Ghosh, S; Rakshit, T; Mukhopadhyay, R

2016-01-01

DNA threading intercalators are a unique class of intercalating agents, albeit little biophysical information is available on their intercalative actions. Herein, the intercalative effects of nogalamycin, which is a naturally-occurring DNA threading intercalator, have been investigated by high-resolution atomic force microscopy (AFM) and spectroscopy (AFS). The results have been compared with those of the well-known chemotherapeutic drug daunomycin, which is a non-threading classical intercalator bearing structural similarity to nogalamycin. A comparative AFM assessment revealed a greater increase in DNA contour length over the entire incubation period of 48 h for nogalamycin treatment, whereas the contour length increase manifested faster in case of daunomycin. The elastic response of single DNA molecules to an externally applied force was investigated by the single molecule AFS approach. Characteristic mechanical fingerprints in the overstretching behaviour clearly distinguished the nogalamycin/daunomycin-treated dsDNA from untreated dsDNA-the former appearing less elastic than the latter, and the nogalamycin-treated DNA distinguished from the daunomycin-treated DNA-the classically intercalated dsDNA appearing the least elastic. A single molecule AFS-based discrimination of threading intercalation from the classical type is being reported for the first time.

Discriminating Intercalative Effects of Threading Intercalator Nogalamycin, from Classical Intercalator Daunomycin, Using Single Molecule Atomic Force Spectroscopy

PubMed Central

Sett, S.; Ghosh, S.; Rakshit, T.; Mukhopadhyay, R.

2016-01-01

DNA threading intercalators are a unique class of intercalating agents, albeit little biophysical information is available on their intercalative actions. Herein, the intercalative effects of nogalamycin, which is a naturally-occurring DNA threading intercalator, have been investigated by high-resolution atomic force microscopy (AFM) and spectroscopy (AFS). The results have been compared with those of the well-known chemotherapeutic drug daunomycin, which is a non-threading classical intercalator bearing structural similarity to nogalamycin. A comparative AFM assessment revealed a greater increase in DNA contour length over the entire incubation period of 48 h for nogalamycin treatment, whereas the contour length increase manifested faster in case of daunomycin. The elastic response of single DNA molecules to an externally applied force was investigated by the single molecule AFS approach. Characteristic mechanical fingerprints in the overstretching behaviour clearly distinguished the nogalamycin/daunomycin-treated dsDNA from untreated dsDNA—the former appearing less elastic than the latter, and the nogalamycin-treated DNA distinguished from the daunomycin-treated DNA—the classically intercalated dsDNA appearing the least elastic. A single molecule AFS-based discrimination of threading intercalation from the classical type is being reported for the first time. PMID:27183010

Absence of photoemission from the Fermi level in potassium intercalated picene and coronene films: structure, polaron, or correlation physics?

PubMed

Mahns, Benjamin; Roth, Friedrich; Knupfer, Martin

2012-04-07

The electronic structure of potassium intercalated picene and coronene films has been studied using photoemission spectroscopy. Picene has additionally been intercalated using sodium. Upon alkali metal addition core level as well as valence band photoemission data signal a filling of previously unoccupied states of the two molecular materials due to charge transfer from potassium. In contrast to the observation of superconductivity in K(x)picene and K(x)coronene (x ~ 3), none of the films studied shows emission from the Fermi level, i.e., we find no indication for a metallic ground state. Several reasons for this observation are discussed.

Hexagonal boron nitride intercalated multi-layer graphene: a possible ultimate solution to ultra-scaled interconnect technology

NASA Astrophysics Data System (ADS)

Li, Yong-Jun; Sun, Qing-Qing; Chen, Lin; Zhou, Peng; Wang, Peng-Fei; Ding, Shi-Jin; Zhang, David Wei

2012-03-01

We proposed intercalation of hexagonal boron nitride (hBN) in multilayer graphene to improve its performance in ultra-scaled interconnects for integrated circuit. The effect of intercalated hBN layer in bilayer graphene is investigated using non-equilibrium Green's functions. We find the hBN intercalated bilayer graphene exhibit enhanced transport properties compared with pristine bilayer ones, and the improvement is attributed to suppression of interlayer scattering and good planar bonding condition of inbetween hBN layer. Based on these results, we proposed a via structure that not only benefits from suppressed interlayer scattering between multilayer graphene, but also sustains the unique electrical properties of graphene when many graphene layers are stacking together. The ideal current density across the structure can be as high as 4.6×109 A/cm2 at 1V, which is very promising for the future high-performance interconnect.

Intercalation complex of proflavine with DNA: Structure and dynamics by solid-state NMR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Pei; Juang, Chilong; Harbison, G.S.

1990-07-06

The structure of the complex formed between the intercalating agent proflavine and fibrous native DNA was studied by one- and two-dimensional high-resolution solid-state nuclear magnetic resonance (NMR). Carbon-13-labeled proflavine was used to show that the drug is stacked with the aromatic ring plane perpendicular to the fiber axis and that it is essentially immobile. Natural abundance carbon-13 NMR of the DNA itself shows that proflavine binding does not change the puckering of the deoxyribose ring. However, phosphorus-31 NMR spectra show profound changes in the orientation of the phosphodiester grouping on proflavine binding, with some of the phosphodiesters tilting almost parallelmore » to the helix axis, and a second set almost perpendicular. The first group to the phosphodiesters probably spans the intercalation sites, whereas the tilting of the second set likely compensates for the unwinding of the DNA by the intercalator.« less

Flattening and manipulation of the electronic structure of h-BN/Rh(111) nanomesh upon Sn intercalation

NASA Astrophysics Data System (ADS)

Sugiyama, Yuya; Bernard, Carlo; Okuyama, Yuma; Ideta, Shin-ichiro; Tanaka, Kiyohisa; Greber, Thomas; Hirahara, Toru

2018-06-01

We have deposited Sn on corrugated hexagonal boron nitride (h-BN) nanomeshs formed on Rh(111) and found that Sn atoms are intercalated between h-BN and Rh, flattening the h-BN. Our reflection high-energy electron diffraction (RHEED) analysis showed that the average in-plane lattice constant of h-BN increases due to the loss of the corrugation. Furthermore, electronic structure measurements based on angle-resolved photoemission spectroscopy (ARPES) showed that the h-BN π band width increases significantly while the σ band width does not change as much. These behaviors were partly different from previous reports on the intercalation of h-BN/Rh system. Our results offer a novel, simple method to control the electronic structure of h-BN.

Synthesis and reversible hydration behavior of the thiosulfate intercalated layered double hydroxide of Zn and Al

DOE Office of Scientific and Technical Information (OSTI.GOV)

Radha, S.; Milius, Wolfgang; Breu, Josef, E-mail: josef.breu@uni-bayreuth.de

2013-08-15

The thiosulfate-intercalated layered double hydroxide of Zn and Al undergoes reversible hydration with a variation in the relative humidity of the ambient. The hydrated and dehydrated phases, which represent the end members of the hydration cycle, both adopt the structure of the 3R{sub 1} polytype. In the intermediate range of relative humidity values (40–60%), the hydrated and dehydrated phases coexist. The end members of the hydration cycle adopt the structure of the same polytype, and vary only in their basal spacings. This points to the possibility that all the intermediate phases have a kinetic origin. - Graphical abstract: Basal spacingmore » evolution of the thiosulfate ion intercalated [Zn–Al] LDH during one complete hydration–dehydration cycle as a function of relative humidity. Display Omitted - Highlights: • Thiosulfate intercalated [Zn–Al] LDHs were synthesized by co-precipitation. • The LDH exhibits reversible hydration with variation in humidity. • Both the end members of the hydration cycle adopt the same polytype structure. • The interstratified intermediates observed are kinetic in origin.« less

Insights into finding a mismatch through the structure of a mispaired DNA bound by a rhodium intercalator

PubMed Central

Pierre, Valérie C.; Kaiser, Jens T.; Barton, Jacqueline K.

2007-01-01

We report the 1.1-Å resolution crystal structure of a bulky rhodium complex bound to two different DNA sites, mismatched and matched in the oligonucleotide 5′-(dCGGAAATTCCCG)2-3′. At the AC mismatch site, the structure reveals ligand insertion from the minor groove with ejection of both mismatched bases and elucidates how destabilized mispairs in DNA may be recognized. This unique binding mode contrasts with major groove intercalation, observed at a matched site, where doubling of the base pair rise accommodates stacking of the intercalator. Mass spectral analysis reveals different photocleavage products associated with the two binding modes in the crystal, with only products characteristic of mismatch binding in solution. This structure, illustrating two clearly distinct binding modes for a molecule with DNA, provides a rationale for the interrogation and detection of mismatches. PMID:17194756

Small molecule-mediated duplex formation of nucleic acids with 'incompatible' backbones.

PubMed

Cafferty, Brian J; Musetti, Caterina; Kim, Keunsoo; Horowitz, Eric D; Krishnamurthy, Ramanarayanan; Hud, Nicholas V

2016-04-07

Proflavine, a known intercalator of DNA and RNA, promotes duplex formation by nucleic acids with natural and non-natural backbones that otherwise form duplexes with low thermal stability, and even some that show no sign of duplex formation in the absence of proflavine. These findings demonstrate the potential for intercalators to be used as cofactors for the assembly of rationally designed nucleic acid structures, and could provide fundamental insights regarding intercalation of natural nucleic acid duplexes.

A molecular model for proflavine-DNA intercalation.

PubMed Central

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. PMID:3174439

Decreasing the electronic confinement in layered perovskites through intercalation.

PubMed

Smith, Matthew D; Pedesseau, Laurent; Kepenekian, Mikaël; Smith, Ian C; Katan, Claudine; Even, Jacky; Karunadasa, Hemamala I

2017-03-01

We show that post-synthetic small-molecule intercalation can significantly reduce the electronic confinement of 2D hybrid perovskites. Using a combined experimental and theoretical approach, we explain structural, optical, and electronic effects of intercalating highly polarizable molecules in layered perovskites designed to stabilize the intercalants. Polarizable molecules in the organic layers substantially alter the optical and electronic properties of the inorganic layers. By calculating the spatially resolved dielectric profiles of the organic and inorganic layers within the hybrid structure, we show that the intercalants afford organic layers that are more polarizable than the inorganic layers. This strategy reduces the confinement of excitons generated in the inorganic layers and affords the lowest exciton binding energy for an n = 1 perovskite of which we are aware. We also demonstrate a method for computationally evaluating the exciton's binding energy by solving the Bethe-Salpeter equation for the exciton, which includes an ab initio determination of the material's dielectric profile across organic and inorganic layers. This new semi-empirical method goes beyond the imprecise phenomenological approximation of abrupt dielectric-constant changes at the organic-inorganic interfaces. This work shows that incorporation of polarizable molecules in the organic layers, through intercalation or covalent attachment, is a viable strategy for tuning 2D perovskites towards mimicking the reduced electronic confinement and isotropic light absorption of 3D perovskites while maintaining the greater synthetic tunability of the layered architecture.

New Lithium- and Diamine-Intercalated Superconductors Lix(CnH2n+4N2)yMoSe2 (n = 2,6)

NASA Astrophysics Data System (ADS)

Sato, Kazuki; Noji, Takashi; Hatakeda, Takehiro; Kawamata, Takayuki; Kato, Masatsune; Koike, Yoji

2018-05-01

We have succeeded in synthesizing new intercalation superconductors Lix(C2H8N2)yMoSe2 and Lix(C6H16N2)yMoSe2 with Tc = 4.2 and 3.8-6.0 K, respectively, via the co-intercalation of lithium and ethylenediamine or hexamethylenediamine into semiconducting 2H-MoSe2. It has been found that the Tc values are related not to the interlayer spacing between MoSe2 layers so much but to the electronic density of states (EDOS) at the Fermi level. Moreover, only Li-intercalated LixMoSe2 with a small interlayer spacing has been found to be non-superconducting. Accordingly, it has been concluded that not only a sufficient amount of EDOS at the Fermi level due to the charge transfer from intercalated Li to MoSe2 layers but also the enhancement of the two-dimensionality of the crystal structure and/or electronic structure due to the expansion of the interlayer spacing between MoSe2 layers is necessary for the appearance of superconductivity in MoSe2-based intercalation superconductors. The pairing mechanism and the analogy to the superconductivity in the electric double-layer transistors of 2H-MoX2 (X = S, Se, Te) are discussed.

Reversible intercalation of ammonia molecules into a layered double hydroxide structure without exchanging nitrate counter-ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carbajal Arizaga, Gregorio Guadalupe, E-mail: gregoriocarbajal@yahoo.com.m; Wypych, Fernando; Castillon Barraza, Felipe

2010-10-15

A zinc/aluminum LDH was precipitated with recycled ammonia from a chemical vapor deposition reaction. The LDH presented a crystalline phase with basal distance of 8.9 A, typical for nitrate-containing LDHs, and another phase with a basal distance of 13.9 A. Thermal treatment at 150 {sup o}C eliminated the phase with the bigger basal distance leaving only the anhydrous nitrate-intercalated LDH structure with 8.9 A. Intense N-H stretching modes in the FTIR spectra suggested that the expansion was due to intercalation of ammonia in the form of [NH{sub 4}(NH{sub 3}){sub n}]{sup +} species. When additional samples were precipitated with pure ammonia,more » the conventional LDH nitrate structure was obtained (8.9 A basal distance) at pH=7, as well as a pure crystalline phase with 13.9 A basal distance at pH=10 due to ammonia intercalation that can be removed by heating at 150 {sup o}C or by stirring in acetone, confirming a unusual sensu stricto intercalation process into a LDH without exchanging nitrate ions. - Graphical abstract: LDH-nitrate precipitated with ammonia expands the interlayer space if ammonia is bubbled up to pH 10. The basal distance decreased when the compound was heated at 150 {sup o}C or stirred in acetone. Nitrate ions are not exchanged.« less

The structure of drug-deoxydinucleoside phosphate complex; generalized conformational behavior of intercalation complexes with RNA and DNA fragments.

PubMed Central

Shieh, H S; Berman, H M; Dabrow, M; Neidle, S

1980-01-01

A 2:2 complex of proflavine and deoxycytidylyl-3', 5'-guanosine has been crystallized and its structure determined by x-ray crystallography. The two dinucleoside phosphate strands form self complementary duplexes with Watson Crick hydrogen bonds. One proflavin is asymmetrically intercalated between the base pairs and the other is stacked above them. The conformations of the nucleotides are unusual in that one strand has C3',C2'endomixed sugar puckering and the other has C3',C3' endo deoxyribose sugars. These results show that the conformation of the 3'sugar is of secondary importance to the intercalated geometry. PMID:7355129

Development of New Elastomers and Elastic Nanocomposites from Plant Oils

NASA Astrophysics Data System (ADS)

Zhu, Lin; Wool, Richard

2006-03-01

Economic and environmental concerns lead to the development of new polymers from renewable resources. In this research, new elastomers were synthesized from plant oil based resins. Acrylated oleic methyl ester (AOME), synthesized from high oleic triglycerides, can readily undergo free radical polymerization and form a linear polymer. To achieve the elastic properties, different strategies have been developed to generate an elastic network and control the crosslink density. The elastomers are reinforced by nanoclays. The intercalated state has a network structure similar to thermoplastic elastomers in which the hard segments aggregate to give ordered crystalline domains. The selected organically modified clay and AOME matrix have similar solubility parameters, therefore intercalation of the monomer/polymer into the clay layers occurs and the nano-scale multilayered structure is stable. In situ intercalation and solution intercalation were used to prepare the elastic nanocomposites. Dramatic improvement in mechanical properties was observed. Changes of tensile strength, strain, Young's modulus and fracture energy were related to the clay concentration. The fracture surface was studied to further understand clay effects on the mechanical properties. Self-Healing of the intercalated nanobeams, thermal stability, biocompatibility and biodegradability of this new elastomer were also explored.

Layered zinc hydroxide nanocones: synthesis, facile morphological and structural modification, and properties

NASA Astrophysics Data System (ADS)

Ma, Wei; Ma, Renzhi; Liang, Jianbo; Wang, Chengxiang; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

2014-10-01

Layered zinc hydroxide nanocones intercalated with DS- have been synthesized for the first time via a convenient synthetic approach, using homogeneous precipitation in the presence of urea and sodium dodecyl sulfate (SDS). SDS plays a significant role in controlling the morphologies of as-synthesized samples. Conical samples intercalated with various anions were transformed through an anion-exchange route in ethanol solution, and the original conical structure was perfectly maintained. Additionally, these DS--inserted nanocones can be transformed into square-like nanoplates in aqueous solution at room temperature, fulfilling the need for different morphology-dependent properties. Corresponding ZnO nanocones and nanoplates have been further obtained through the thermal calcination of NO3--intercalating zinc hydroxide nanocones/nanoplates. These ZnO nanostructures with different morphologies exhibit promising photocatalytic properties.Layered zinc hydroxide nanocones intercalated with DS- have been synthesized for the first time via a convenient synthetic approach, using homogeneous precipitation in the presence of urea and sodium dodecyl sulfate (SDS). SDS plays a significant role in controlling the morphologies of as-synthesized samples. Conical samples intercalated with various anions were transformed through an anion-exchange route in ethanol solution, and the original conical structure was perfectly maintained. Additionally, these DS--inserted nanocones can be transformed into square-like nanoplates in aqueous solution at room temperature, fulfilling the need for different morphology-dependent properties. Corresponding ZnO nanocones and nanoplates have been further obtained through the thermal calcination of NO3--intercalating zinc hydroxide nanocones/nanoplates. These ZnO nanostructures with different morphologies exhibit promising photocatalytic properties. Electronic supplementary information (ESI) available: Typical SEM images, TGA curves and XRD patterns of as-prepared samples. See DOI: 10.1039/c4nr04166f

H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Fronko, R. M.; Resing, H. A.; Qian, X. W.; Solin, S. A.

1987-01-01

For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.

Controlled release formulation of an anti-depression drug based on a L-phenylalanate-zinc layered hydroxide intercalation compound

NASA Astrophysics Data System (ADS)

Hashim, Norhayati; Sharif, Sharifah Norain Mohd; Isa, Illyas Md; Hamid, Shahidah Abdul; Hussein, Mohd Zobir; Bakar, Suriani Abu; Mamat, Mazidah

2017-06-01

The intercalation of L-phenylalanate (LP) into the interlayer gallery of zinc layered hydroxide (ZLH) has been successfully executed using a simple direct reaction method. The synthesised intercalation compound, zinc layered hydroxide-L-phenylalanate (ZLH-LP), was characterised using PXRD, FTIR, CHNS, ICP-OES, TGA/DTG, FESEM and TEM. The PXRD patterns of the intercalation compound demonstrate an intense and symmetrical peak, indicating a well-ordered crystalline layered structure. The appearance of an intercalation peak at a low angle of 2θ with a basal spacing of 16.3 Å, signifies the successful intercalation of the L-phenylalanate anion into the interlayer gallery of the host. The intercalation is also validated by FTIR spectroscopy and CHNS elemental analysis. Thermogravimetric analysis confirms that the ZLH-LP intercalation compound has higher thermal stability than the pristine L-phenylalanine. The observed percentage of L-phenylalanate accumulated release varies in each release media, with 84.5%, 79.8%, 63.8% and 61.8% release in phosphate buffer saline (PBS) solution at pH 4.8, deionised water, PBS solution at pH 7.4 and NaCl solution, respectively. The release behaviour of LP from its intercalation compounds in deionised water and PBS solution at pH 4.8 follows pseudo second order, whereas in NaCl solution and PBS solution at pH 7.4, it follows the parabolic diffusion model. This study shows that the synthesised ZLH-LP intercalation compound can be used for the formation of a new generation of materials for targeted drug release with controlled release properties.

The staging mechanism of AlCl4 intercalation in a graphite electrode for an aluminium-ion battery.

PubMed

Bhauriyal, Preeti; Mahata, Arup; Pathak, Biswarup

2017-03-15

Identifying a suitable electrode material with desirable electrochemical properties remains a primary challenge for rechargeable Al-ion batteries. Recently an ultrafast rechargeable Al-ion battery was reported with high charge/discharge rate, (relatively) high discharge voltage and high capacity that uses a graphite-based cathode. Using calculations from first-principles, we have investigated the staging mechanism of AlCl 4 intercalation into bulk graphite and evaluated the stability, specific capacity and voltage profile of AlCl 4 intercalated compounds. Ab initio molecular dynamics is performed to investigate the thermal stability of AlCl 4 intercalated graphite structures. Our voltage profiles show that the first AlCl 4 intercalation step could be a more sluggish step than the successive intercalation steps. However, the diffusion of AlCl 4 is very fast in the expanded graphite host layers with a diffusion barrier of ∼0.01 eV, which justifies the ultrafast charging rate of a graphite based Al-ion battery. And such an AlCl 4 intercalated battery provides an average voltage of 2.01-2.3 V with a maximum specific capacity of 69.62 mA h g -1 , which is excellent for anion intercalated batteries. Our density of states and Bader charge analysis shows that the AlCl 4 intercalation into the bulk graphite is a charging process. Hence, we believe that our present study will be helpful in understanding the staging mechanism of AlCl 4 intercalation into graphite-like layered electrodes for Al-ion batteries, thus encouraging further experimental work.

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction

PubMed Central

Wang, Haotian; Lu, Zhiyi; Xu, Shicheng; Kong, Desheng; Cha, Judy J.; Zheng, Guangyuan; Hsu, Po-Chun; Yan, Kai; Bradshaw, David; Prinz, Fritz B.; Cui, Yi

2013-01-01

The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li+ ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity. PMID:24248362

Understanding self-photorechargeability of WO(3) for H(2) generation without light illumination.

PubMed

Ng, Charlene; Iwase, Akihide; Ng, Yun Hau; Amal, Rose

2013-02-01

This work presents insight into the self-photorechargeability of WO(3), whereby the intercalation of positive alkali cations is accompanied by the simultaneous storage of photo-excited electrons. The cyclic voltammetry studies verify the photo-assisted intercalation and de-intercalation of Na(+) and K(+) from the flower structured WO(3). A storage capacity of up to 0.722 C cm(-2) can be achieved in a saturated (0.68 M) K(2)SO(4) electrolyte solution. However, the best photo recharge-discharge stability of the electrode are observed at a lower (0.1 M) cation concentration. At high electrolyte concentrations, the intercalated cations are firmly trapped, as indicated by the structural modifications observed in Raman analysis, resulting in much less photocharging and discharging abilities in subsequent cycles. The study also shows that the stored electrons can be successfully used to generate H(2) with 100 % faradaic efficiency in the absence of light. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of mixed-layer structures in smectites intercalated with tryptone

NASA Astrophysics Data System (ADS)

Block, K. A.; Trusiak, A.; Steiner, J. C.; Katz, A.; Gottlieb, P.; Alimova, A.

2012-12-01

Stable clay-protein complexes are fundamental to studies of the critical zone, terrestrial ecosystems, pharmacology, and industrial applications such as bioremediation. Two sets of montmorillonite clays were purified and made homoionic for Na and Mg. Mg-montmorillonite and Na-montmorillonite were mixed with tryptone (casein digest) in a 9:1 and 18:1 clay:tryptone ratio, resulting in the formation of reversible intercalated structures. X-ray diffraction analysis of the protein-clay complexes produced profiles consisting of two peaks associated with the smectite 001 reflection and a related tryptone-packet peak similar to that produced by a mixed layer clay structure. Shifts in the 002, 003, and 004 diffraction maxima are attributed to disorder caused by the interaction with the protein. Line broadening in the smectite-tryptone XRD spectra is interpreted to be the result of interlayer absorption. Adsorption produces coherent crystalline packets of regularly interbedded tryptone and smectite platelets. SEM images reveal clay platelets with upwardly rolled edges that tend toward cylindrical structures with the production of occasional tubes in the smaller platelet size range as noted for organic compound-kaolinite intercalation reported by Fenoll Hach-Ali and Weiss (1969). Reference: Fenoll Hach-Ali, P.F., Weiss, A., 1969. Estudio de la reaccion de caolinita y N-metilform- amida. Quimica LXV, 769-790. Scanning electron micrograph of tryptone-intercalated clay platelets exhibiting rolled edge structure.

Unified picture of the doping dependence of superconducting transition temperatures in alkali metal/ammonia intercalated FeSe

NASA Astrophysics Data System (ADS)

Guterding, Daniel; Jeschke, Harald; Hirschfeld, Peter; Valenti, Roser

2015-03-01

We present a theoretical investigation of alkali metal/ammonia intercalated iron selenide. Using ab-initio density functional theory we unravel how charge doping and dimensionality of the electronic structure can be controlled through the chemical composition of the intercalated molecules. Within random phase approximation spin fluctuation theory we analyze the impact of intercalation on the superconducting pairing strength. We find that high Tc is to be expected away from perfect nesting. While experimental studies have focused on the intercalation of larger molecules in the spacer layer so far, we argue that no higher Tc can be achieved this way. This work was supported by Deutsche Forschungsgemeinschaft under Grant No. SPP 1458, the National Science Foundation under Grant No. PHY11-25915 and the Department of Energy under Grant No. DE-FG02-05ER46236.

Intercalation of paracetamol into the hydrotalcite-like host

NASA Astrophysics Data System (ADS)

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.

Synthesis and characterization of intercalated polyaniline-clay nanocomposite using supercritical CO2

NASA Astrophysics Data System (ADS)

Abdelraheem, A.; El-Shazly, A. H.; Elkady, M. F.

2018-05-01

Lately, supercritical CO2 (SCCO2) have been getting great interest. It can be used in numerous applications because it is environmentally friendly, safe, comparatively low cost, and nonflammable. One of its applications is being a solvent in the synthesis of polymeric-clay nanocomposite. In this paper, intercalated polyaniline-clay nanocomposite (PANC) was prepared using SCCO2. The intercalation structure of polyaniline chains between clay layers was verified by various characterization techniques. Scanning electron microscope and transmission electron microscope (SEM-TEM) were used to show the morphology of the synthesized nanocomposite. The molecular structure of PANC nanocomposite was confirmed using Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The BET surface area and the conductivity of the nanocomposite were determined.

Structural and thermal properties of inorganic-organic montmorillonite: Implications for their potential environmental applications.

PubMed

Rathnayake, Suramya I; Xi, Yunfei; Frost, Ray L; Ayoko, Godwin A

2015-12-01

Inorganic-organic clays (IOCs), clays intercalated with both organic cations such as cationic surfactants and inorganic cations such as metal hydroxy polycations have the properties of both organic and pillared clays, and thereby the ability to remove both inorganic and organic contaminants from water simultaneously. In this study, IOCs were synthesised using three different methods with different surfactant concentrations. Octadecyltrimethylammonium bromide (ODTMA) and hydroxy aluminium ([Al13O4(OH)24(H2O)12](7+) or Al13) are used as the organic and inorganic modifiers (intercalation agents). According to the results, the interlayer distance, the surfactant loading amount and the Al/Si ratio of IOCs strictly depend on the intercalation method and the intercalation agent ratio. Interlayers of IOCs synthesised by intercalating ODTMA before Al13 and IOCs synthesised by simultaneous intercalation of ODTMA and Al13 were increased with increasing the ODTMA concentration used in the synthesis procedure and comparatively high loading amounts could be observed in them. In contrast, Al/Si decreased with increasing ODTMA concentration in these two types of IOCs. The results suggest that Al-pillars can be fixed within the interlayers by calcination and any increment in the amount of ODTMA used in the synthesis procedure did not affect the interlayer distance of the IOCs. Overall the study provides valuable insights into the structure and properties of the IOCs and their potential environmental applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Antiproliferative, DNA intercalation and redox cycling activities of dioxonaphtho[2,3-d]imidazolium analogs of YM155: A structure-activity relationship study.

PubMed

Ho, Si-Han Sherman; Sim, Mei-Yi; Yee, Wei-Loong Sherman; Yang, Tianming; Yuen, Shyi-Peng John; Go, Mei-Lin

2015-11-02

The anticancer agent YM155 is widely investigated as a specific survivin suppressant. More recently, YM155 was found to induce DNA damage and this has raised doubts as to whether survivin is its primary target. In an effort to assess the contribution of DNA damage to the anticancer activity of YM155, several analogs were prepared and evaluated for antiproliferative activity on malignant cells, participation in DNA intercalation and free radical generation by redox cycling. The intact positively charged scaffold was found to be essential for antiproliferative activity and intercalation but was less critical for redox cycling where the minimal requirement was a pared down bicyclic quinone. Side chain requirements at the N(1) and N(3) positions of the scaffold were more alike for redox cycling and intercalation than antiproliferative activity, underscoring yet again, the limited structural overlaps for these activities. Furthermore, antiproliferative activities were poorly correlated to DNA intercalation and redox cycling. Potent antiproliferative activity (IC50 9-23 nM), exceeding that of YM155, was found for a minimally substituted methyl analog AB7. Like YM155 and other dioxonaphthoimidazoliums, AB7 was a modest DNA intercalator but with weak redox cycling activity. Thus, the capacity of this scaffold to inflict direct DNA damage leading to cell death may not be significant and YM155 should not be routinely classified as a DNA damaging agent. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Intercalated organic-inorganic perovskites stabilized by fluoroaryl-aryl interactions.

PubMed

Mitzi, David B; Medeiros, David R; Malenfant, Patrick R L

2002-04-22

Crystals of several new hybrid tin(II) iodide-based perovskites, involving 2,3,4,5,6- pentafluorophenethylammonium or phenethylammonium cation bilayers and intercalated aryl or perfluoroaryl molecules, were grown by slow evaporation of a methanol solution containing the hybrid perovskite and the intercalating species. The (C(6)F(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)H(6)) structure was solved at -75 degrees C in a monoclinic C2/c subcell [a = 41.089(12) A, b = 6.134(2) A, c = 12.245(3) A, beta = 94.021(5) degrees, Z = 4] and consists of sheets of corner-sharing distorted SnI(6) octahedra separated by bilayers of pentafluorophenethylammonium cations. The intercalated benzene molecules form a single well-ordered layer interposed between adjacent fluoroaryl cation layers. The corresponding hybrid with an unfluorinated organic cation and fluorinated intercalating molecule, (C(6)H(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)F(6)), is isostructural [a = 40.685(4) A, b = 6.0804(6) A, c = 12.163(1) A, beta = 93.136(2) degrees, Z = 4]. For each intercalated system, close C...C contacts (3.44-3.50 A) between the aromatic cation and the intercalated molecule are indicative of a significant face-to-face interaction, similar to that found in the complex C(6)H(6).C(6)F(6). Crystal growth runs with the organic cation and prospective intercalating molecule either both fluorinated or both unfluorinated did not yield stable intercalated compounds, demonstrating the significance of fluoroaryl-aryl interactions in the current intercalated structures. Thermal analysis of (C(6)F(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)H(6)) and (C(6)H(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)F(6)) crystals yields, in addition to the characteristic transitions of the parent perovskite, endothermic transitions [12.6(5) and 32.1(8) kJ/mol, respectively] with an onset at 145 degrees C and a weight loss corresponding to the complete loss of the intercalated molecule. The relatively high deintercalation temperature (well above the boiling point of benzene and hexafluorobenzene) demonstrates the usefulness of the hybrid perovskites in providing a stable framework for the examination of the fluoroaryl-aryl interaction, as well as the potential importance of this interaction in tailoring new hybrid perovskites. UV-vis absorption measurements on (C(6)H(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)F(6)) thin films indicate a small reversible wavelength shift to higher energy for the tin(II) iodide framework exciton peak (with respect to that of the parent perovskite spectrum), from 608(2) nm [2.04 eV] to 595(2) nm [2.08 eV], and a corresponding shift in the band edge position. This spectral shift can most reasonably be attributed to subtle structural changes induced in the tin(II) iodide sheets by the intercalated hexafluorobenzene molecules.

Atomic-scale recognition of surface structure and intercalation mechanism of Ti3C2X.

PubMed

Wang, Xuefeng; Shen, Xi; Gao, Yurui; Wang, Zhaoxiang; Yu, Richeng; Chen, Liquan

2015-02-25

MXenes represent a large family of functionalized two-dimensional (2D) transition-metal carbides and carbonitrides. However, most of the understanding on their unique structures and applications stops at the theoretical suggestion and lack of experimental support. Herein, the surface structure and intercalation chemistry of Ti3C2X are clarified at the atomic scale by aberration-corrected scanning transmission electron microscope (STEM) and density functional theory (DFT) calculations. The STEM studies show that the functional groups (e.g., OH(-), F(-), O(-)) and the intercalated sodium (Na) ions prefer to stay on the top sites of the centro-Ti atoms and the C atoms of the Ti3C2 monolayer, respectively. Double Na-atomic layers are found within the Ti3C2X interlayer upon extensive Na intercalation via two-phase transition and solid-solution reactions. In addition, aluminum (Al)-ion intercalation leads to horizontal sliding of the Ti3C2X monolayer. On the basis of these observations, the previous monolayer surface model of Ti3C2X is modified. DFT calculations using the new modeling help to understand more about their physical and chemical properties. These findings enrich the understanding of the MXenes and shed light on future material design and applications. Moreover, the Ti3C2X exhibits prominent rate performance and long-term cycling stability as an anode material for Na-ion batteries.

Synthesis and characterization of montmorillonite clay intercalated with molecular magnetic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martins, Marcel G.; Martins, Daniel O.T.A.; Carvalho, Beatriz L.C. de

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 spacemore » 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.« less

Electronic and Structural Studies of Intercalated Graphite and Buckminsterfullerene.

NASA Astrophysics Data System (ADS)

Kelty, Stephen Paul

Under the direction of Prof. C. M. Lieber, the surface electronic and structural properties of binary MC_{rm x} and ternary rm MM^' C_{x } donor graphite intercalation compounds (GICs) were investigated using scanning tunneling microscopy (STM) and other surface sensitive techniques. The STM images revealed previously unobserved superstructures in the local density of states contours. These new superstructures include a commensurate 4.9 A periodicity (MC_8, where M = Li, K, Rb, Cs, KHg, rm K_2Hg_2 and rm K_2Tl _3). This superstructure has been interpreted as a modulation of the surface density of states due to the underlying commensurate intercalate lattice. Other GICs exhibit longer wavelength incommensurate superstructures, including: 19 A rm (KH_{0.8}C _8), 12 A rm (KH_{0.8 }C_4), 8.9 A rm (KHgC _4) and 7.5 A rm (KTl_ {1.5}C_8) periodicities. The direct -space wavelength of these incommensurate superstructures was found to scale inversely with the amount of charge transferred from the intercalate to the graphite layers. Such a correlation is consistent with the wavelength dependence on Fermi surface expansion of a charge density wave (CDW) state. STM investigations of adsorbed films of colloidal BiI_3, prepared by a solution-phase method, revealed the presence of mono-disperse 10-50 A single-layer particles with atomic resolution. This investigation demonstrated both the validity of the preparative method for the BiI_3 particles and the capability of the STM to atomically resolve small semiconducting particles. The structural and superconducting properties of alkali metal intercalated Buckminsterfullerene (C _{60}) were also investigated. A new preparatory method was developed using heavy metal alloys instead of pure alkali metal. Using these alloys, it was discovered that high superconducting fraction intercalation compounds could be prepared under milder conditions than by using the pure alkali metal. In addition, intercalation of Hg, Tl and Bi alloys of Cs was found to form a superconducting phase which has never been prepared by direct intercalation of Cs metal. Finally, other investigators have empirically derived a linear dependence of T_{ rm c} on lattice constant for intercalated C_{60}. This dependence has been used to model the electron pairing mechanism for the superconducting state. Investigations presented herein indicate that for lattice constants greater than 14.5 A, no further increases in T_{rm c} are observed. This finding places constraints on the above mentioned electron pairing models.

Intercalation of Coordinatively Unsaturated Fe(III) Ion within Interpenetrated Metal-Organic Framework MOF-5.

PubMed

Holmberg, Rebecca J; Burns, Thomas; Greer, Samuel M; Kobera, Libor; Stoian, Sebastian A; Korobkov, Ilia; Hill, Stephen; Bryce, David L; Woo, Tom K; Murugesu, Muralee

2016-06-01

Coordinatively unsaturated Fe(III) metal sites were successfully incorporated into the iconic MOF-5 framework. This new structure, Fe(III) -iMOF-5, is the first example of an interpenetrated MOF linked through intercalated metal ions. Structural characterization was performed with single-crystal and powder XRD, followed by extensive analysis by spectroscopic methods and solid-state NMR, which reveals the paramagnetic ion through its interaction with the framework. EPR and Mössbauer spectroscopy confirmed that the intercalated ions were indeed Fe(III) , whereas DFT calculations were employed to ascertain the unique pentacoordinate architecture around the Fe(III) ion. Interestingly, this is also the first crystallographic evidence of pentacoordinate Zn(II) within the MOF-5 SBU. This new MOF structure displays the potential for metal-site addition as a framework connector, thus creating further opportunity for the innovative development of new MOF materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure, molecular simulation, and release of aspirin from intercalated Zn-Al-layered double hydroxides.

PubMed

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Local corrugation and persistent charge density wave in ZrTe 3 with Ni intercalation

NASA Astrophysics Data System (ADS)

Ganose, Alex M.; Gannon, Liam; Fabrizi, Federica; Nowell, Hariott; Barnett, Sarah A.; Lei, Hechang; Zhu, Xiangde; Petrovic, Cedomir; Scanlon, David O.; Hoesch, Moritz

2018-04-01

The mechanism of emergent bulk superconductivity in transition-metal intercalated ZrTe3 is investigated by studying the effect of Ni doping on the band structure and charge density wave (CDW). The study reports theoretical and experimental results in the range of Ni0.01ZrTe3 to Ni0.05ZrTe3 . In the highest doped samples, bulk superconductivity with Tc

Antisite occupation induced single anionic redox chemistry and structural stabilization of layered sodium chromium sulfide

DOE PAGES

Shadike, Zulipiya; Zhou, Yong -Ning; Chen, Lan -Li; ...

2017-08-30

The intercalation compounds with various electrochemically active or inactive elements in the layered structure have been the subject of increasing interest due to their high capacities, good reversibility, simple structures and ease of synthesis. However, their reversible intercalation/deintercalation redox chemistries in all previous compounds involve a single cationic redox reaction or a cumulative cationic and anionic redox reaction. Here we report an anionic redox only chemistry and structural stabilization of layered sodium chromium sulfide. It is discovered that sulfur in sodium chromium sulfide is electrochemical active undergoing oxidation/reduction of sulfur rather than chromium. Significantly, sodium ions can successfully move outmore » and into without changing its lattice parameter c, which is explained in terms of the occurrence of chromium/sodium vacancy antisite during desodiation and sodiation processes. Here, our present work not only enriches the electrochemistry of layered intercalation compounds, but also extends the scope of investigation on high-capacity electrodes.« less

Antisite occupation induced single anionic redox chemistry and structural stabilization of layered sodium chromium sulfide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shadike, Zulipiya; Zhou, Yong -Ning; Chen, Lan -Li

The intercalation compounds with various electrochemically active or inactive elements in the layered structure have been the subject of increasing interest due to their high capacities, good reversibility, simple structures and ease of synthesis. However, their reversible intercalation/deintercalation redox chemistries in all previous compounds involve a single cationic redox reaction or a cumulative cationic and anionic redox reaction. Here we report an anionic redox only chemistry and structural stabilization of layered sodium chromium sulfide. It is discovered that sulfur in sodium chromium sulfide is electrochemical active undergoing oxidation/reduction of sulfur rather than chromium. Significantly, sodium ions can successfully move outmore » and into without changing its lattice parameter c, which is explained in terms of the occurrence of chromium/sodium vacancy antisite during desodiation and sodiation processes. Here, our present work not only enriches the electrochemistry of layered intercalation compounds, but also extends the scope of investigation on high-capacity electrodes.« less

Ferric chloride-graphite intercalation compounds as anode materials for Li-ion batteries.

PubMed

Wang, Lili; Zhu, Yongchun; Guo, Cong; Zhu, Xiaobo; Liang, Jianwen; Qian, Yitai

2014-01-01

Ferric chloride-graphite intercalation compounds (FeCl3 -GICs) with stage 1 and stage 2 structures were synthesized by reacting FeCl3 and expanded graphite (EG) in air in a stainless-steel autoclave. As rechargeable Li-ion batteries, these FeCl3 -GICs exhibit high capacity, excellent cycling stability, and superior rate capability, which could be attributed to their unique intercalation features. This work may enable new possibilities for the fabrication of Li-ion batteries. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-state chelation of metal ions by ethylenediaminetetraacetate intercalated in a layered double hydroxide.

PubMed

Tarasov, Konstantin A; O'Hare, Dermot; Isupov, Vitaly P

2003-03-24

The solid-state chelation of transition metal ions (Co(2+), Ni(2+), and Cu(2+)) from aqueous solutions into the lithium aluminum layered double hydroxide ([LiAl(2)(OH)(6)]Cl x 0.5H(2)O or LDH) which has been pre-intercalated with EDTA (ethylenediaminetetraacetate) ligand has been investigated. The intercalated metal cations form [M(edta)](2)(-) complexes between the LDH layers as indicated by elemental analysis, powder X-ray diffraction, and IR and UV-vis spectroscopies. If metal chloride or nitrate salts are used in the reaction with the LDH then co-intercalation of either the Cl(-) or NO(3)(-) anions is observed. In the case of metal acetate salts the cations intercalate without the accompanying anion. This can be explained by the different intercalation selectivity of the anions in relation to the LDH. In the latter case the introduction of the positive charge into LDH structure was compensated for by the release from the solid of the equivalent quantity of lithium and hydrogen cations. Time-resolved in-situ X-ray diffraction measurements have revealed that the chelation/intercalation reactions proceed very quickly. The rate of the reaction found for nickel acetate depends on concentration as approximately k[Ni(Ac)(2)](3).

Modification and intercalation of layered zirconium phosphates: a solid-state NMR monitoring.

PubMed

Bakhmutov, Vladimir I; Kan, Yuwei; Sheikh, Javeed Ahmad; González-Villegas, Julissa; Colón, Jorge L; Clearfield, Abraham

2017-07-01

Several layered zirconium phosphates treated with Zr(IV) ions, modified by monomethoxy-polyethyleneglycol-monophosphate and intercalated with doxorubicin hydrochloride have been studied by solid-state MAS NMR techniques. The organic components of the phosphates have been characterized by the 13 C{ 1 H} CP MAS NMR spectra compared with those of initial compounds. The multinuclear NMR monitoring has provided to establish structure and covalent attachment of organic/inorganic moieties to the surface and interlayer spaces of the phosphates. The MAS NMR experiments including kinetics of proton-phosphorus cross polarization have resulted in an unusual structure of zirconium phosphate 6 combining decoration of the phosphate surface by polymer units and their partial intercalation into the interlayer space. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Density-functional studies of tungsten trioxide, tungsten bronzes, and related systems

NASA Astrophysics Data System (ADS)

Ingham, B.; Hendy, S. C.; Chong, S. V.; Tallon, J. L.

2005-08-01

Tungsten trioxide adopts a variety of structures which can be intercalated with charged species to alter the electronic properties, thus forming “tungsten bronzes.” Similar effects are observed upon removing oxygen from WO3 . We present a computational study of cubic and hexagonal alkali bronzes and examine the effects on cell size and band structure as the size of the intercalated ion is increased. With the exception of hydrogen (which is predicted to be unstable as an intercalate), the behavior of the bronzes are relatively consistent. NaWO3 is the most stable of the cubic systems, although in the hexagonal system the larger ions are more stable. The band structures are identical, with the intercalated atom donating its single electron to the tungsten 5d valence band. A study of fractional doping in the NaxWO3 system (0⩽x⩽1) showed a linear variation in cell parameter and a systematic shift in the Fermi level into the conduction band. In the oxygen-deficient WO3-x system the Fermi level undergoes a sudden jump into the conduction band at around x=0.2 . Lastly, three compounds of a layered WO4•α,ω -diaminoalkane hybrid series were studied and found to be insulating, with features in the band structure similar to those of the parent WO3 compound that relate well to experimental UV-visible spectroscopy results.

Electrochemical behavior of LiV3O8 positive electrode in hybrid Li,Na-ion batteries

NASA Astrophysics Data System (ADS)

Maletti, S.; Sarapulova, A.; Tsirlin, A. A.; Oswald, S.; Fauth, F.; Giebeler, L.; Bramnik, N. N.; Ehrenberg, H.; Mikhailova, D.

2018-01-01

Vanadium(V)-containing oxides show superior intercalation properties for alkaline ions, although the performance of the material strongly depends on its surface morphology. In this work, intercalation activity of LiV3O8, prepared by a conventional solid state synthesis, is demonstrated for the first time in non-aqueous Li,Na-ion hybrid batteries with Na as negative electrode, and different Na/Li ratios in the electrolyte. In the pure Na-ion cell, one Na per formula unit of LiV3O8 can be reversibly inserted at room temperature via a two-step process, while further intercalation leads to gradual amorphisation of the material, with a specific capacity of 190 mAhg-1 after 10 cycles in the potential window of 0.8-3.4 V. Hybrid Li,Na-ion batteries feature simultaneous intercalation of Li+ and Na+ cations into LiV3O8, resulting in the formation of a second phase. Depending on the electrolyte composition, this second phase bears structural similarities either to Li0.7Na0.7V3O8 in Na-rich electrolytes, or to Li4V3O8 in Li-rich electrolytes. The chemical diffusion coefficients of Na+ and Li+ in crystalline LiV3O8 are very close, hence explaining the co-intercalation of these cations. As DFT calculations show, once formed, the Li0.7Na0.7V3O8-type structure favors intercalation of Na+, whereas the LiV3O8-type prefers to accommodate Li+ cations.

Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yadav, Gautam G.; Gallaway, Joshua W.; Turney, Damon E.

2017-03-06

Manganese dioxide cathodes are inexpensive and have high theoretical capacity (based on two electrons) of 617 mAh g-1, making them attractive for low-cost, energy-dense batteries. They are used in non-rechargeable batteries with anodes like zinc. Only ~10% of the theoretical capacity is currently accessible in rechargeable alkaline systems. Attempts to access the full capacity using additives have been unsuccessful. We report a class of Bi-birnessite (a layered manganese oxide polymorph mixed with bismuth oxide (Bi2O3)) cathodes intercalated with Cu2+ that deliver near-full two-electron capacity reversibly for >6,000 cycles. The key to rechargeability lies in exploiting the redox potentials of Cumore » to reversibly intercalate into the Bi-birnessite-layered structure during its dissolution and precipitation process for stabilizing and enhancing its charge transfer characteristics. This process holds promise for other applications like catalysis and intercalation of metal ions into layered structures. A large prismatic rechargeable Zn-birnessite cell delivering ~140 Wh l-1 is shown.« less

Electron doping through lithium intercalation to interstitial channels in tetrahedrally bonded SiC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakai, Yuki; Center for Computational Materials, Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, Texas 78712; Oshiyama, Atsushi

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-ionmore » battery.« less

Direct observation of strain-induced orbital valence band splitting in HfSe2 by sodium intercalation

NASA Astrophysics Data System (ADS)

Eknapakul, T.; Fongkaew, I.; Siriroj, S.; Jindata, W.; Chaiyachad, S.; Mo, S.-K.; Thakur, S.; Petaccia, L.; Takagi, H.; Limpijumnong, S.; Meevasana, W.

2018-05-01

By using angle-resolved photoemission spectroscopy (ARPES), the variation of the electronic structure of HfSe2 has been studied as a function of sodium intercalation. We observe how this drives a band splitting of the p -orbital valence bands and a simultaneous reduction of the indirect band gap by values of up to 400 and 280 meV, respectively. Our calculations indicate that such behavior is driven by the band deformation potential, which is a result of our observed strain induced by sodium intercalation. The applied uniaxial strain calculations based on density functional theory agree strongly with the experimental ARPES data. These findings should assist in studying the physical relationship between intercalation and strain, as well as for large-scale two-dimensional straintronics.

Intercalation of biomolecules into NiAl-NO 3 layered double hydroxide films synthesized in situ on anodic alumina/aluminium support

NASA Astrophysics Data System (ADS)

Zhao, Hua-Zhang; Chang, Ying-Yue; Yang, Jing; Yang, Qin-Zheng

2013-03-01

Layered double hydroxide (LDH) films were synthesized in situ on anodic alumina/aluminium (AAO/Al). Glucose oxidase (GOD) and L-ascorbic acid (vitamin C, VC) were intercalated respectively into the in-situ grown LDH films by anion-exchange in aqueous solutions. Dodecylsulfate (SDS) was used to expand the lamellar structure before GOD intercalation into the LDH film. The resulting products were characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and thermo gravimetric analysis (TGA). The results showed that VC and GOD were successfully intercalated into the in-situ synthesized LDH film. These biomolecules loaded LDH films could have potential applications in electrode modification, safe storage and effective delivery of bioactive compounds.

First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Kaneko, Tomoaki; Saito, Riichiro

2017-11-01

Energetics and electronic structures of alkali metal (Li, Na, K, Rb, and Cs) and alkaline earth metal (Be, Mg, Ca, Sr, and Ba) atoms intercalated bilayer graphene are systematically investigated using first-principles calculations based on density functional theory. Formation of alkali and alkaline earth metal atoms intercalated bilayer graphene is exothermic except for Be and Mg. The interlayer state between two graphene layers is occupied for K, Rb, Cs, Ca, Sr, and Ba. We find that the energetic position of the interlayer states between bilayer graphene monotonically shifts downward with increasing of interlayer distance. The interlayer distances of more than 4.5 Å and 4.0 Å, respectively, are necessary for the occupation of the interlayer state in bilayer graphene for alkali and alkaline earth metal atoms, which is almost independent of the intercalant metal species. We discuss the relevance to occurrence of superconductivity for the metal intercalated bilayer graphene in terms of the occupation of the interlayer state and the phonon frequency of metal ions.

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

Localized concentration reversal of lithium during intercalation into nanoparticles

PubMed Central

Zhang, Wei; Yu, Hui-Chia; Wu, Lijun; Liu, Hao; Abdellahi, Aziz; Qiu, Bao; Bai, Jianming; Orvananos, Bernardo; Strobridge, Fiona C.; Zhou, Xufeng; Liu, Zhaoping; Ceder, Gerbrand; Zhu, Yimei; Thornton, Katsuyo; Grey, Clare P.; Wang, Feng

2018-01-01

Nanoparticulate electrodes, such as LixFePO4, have unique advantages over their microparticulate counterparts for the applications in Li-ion batteries because of the shortened diffusion path and access to nonequilibrium routes for fast Li incorporation, thus radically boosting power density of the electrodes. However, how Li intercalation occurs locally in a single nanoparticle of such materials remains unresolved because real-time observation at such a fine scale is still lacking. We report visualization of local Li intercalation via solid-solution transformation in individual LixFePO4 nanoparticles, enabled by probing sub-angstrom changes in the lattice spacing in situ. The real-time observation reveals inhomogeneous intercalation, accompanied with an unexpected reversal of Li concentration at the nanometer scale. The origin of the reversal phenomenon is elucidated through phase-field simulations, and it is attributed to the presence of structurally different regions that have distinct chemical potential functions. The findings from this study provide a new perspective on the local intercalation dynamics in battery electrodes. PMID:29340302

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

NASA Astrophysics Data System (ADS)

Watanabe, Mebae; Fujihara, Shinobu

2014-02-01

Inorganic-organic layered rare-earth compounds were synthesized on the basis of a biphasic liquid-liquid system in one pot. Layered yttrium hydroxides (LYHs) were chosen as a host material for the intercalation of hydrophobic organic guest anions such as benzoate, sebacate, or laurate. In a typical synthesis, an organic phase dissolving carboxylic acid was placed in contact with an equal amount of an aqueous phase dissolving yttrium nitrate n-hydrate and urea. At elevated temperatures up to 80 °C, urea was hydrolyzed to release hydroxyl anions which were used to form yttrium hydroxide layers. LYHs were then precipitated with the intercalation of carboxylate anions delivered from the organic phase under the distribution law. The structure and the morphology of the LYHs could be modulated by the intercalated anions. Doped with Eu3+ ions, the LYHs exhibited red photoluminescence which was enhanced by the intercalated anions due to the antenna effect.

Preparation of nanostructured and nanosheets of MoS2 oxide using oxidation method.

PubMed

Amini, Majed; Ramazani S A, Ahmad; Faghihi, Morteza; Fattahpour, Seyyedfaridoddin

2017-11-01

Molybdenum disulfide (MoS 2 ), a two-dimensional transition metal has a 2D layered structure and has recently attracted attention due to its novel catalytic properties. In this study, MoS 2 has been successfully intercalated using chemical and physical intercalation techniques, while enhancing its surface properties. The final intercalated MoS 2 is of many interests because of its low-dimensional and potential properties in in-situ catalysis. In this research, we report different methods to intercalate the layers of MoS 2 successfully using acid-treatment, ultrasonication, oxidation and thermal shocking. The other goal of this study is to form SO bonds mainly because of expected enhanced in-situ catalytic operations. The intercalated MoS 2 is further characterized using analyses such as Fourier Transform Infrared Spectroscopy (FTIR), Raman, Contact Angle, X-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), Energy Dispersive X-Ray Microanalysis (EDAX), Transmission electron microscopy (TEM), and BET. Copyright © 2017. Published by Elsevier B.V.

Ferrix Chloride-Graphite Intercalation Compounds Prepared From Graphite Flouride

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1995-01-01

The reaction between graphite fluoride and ferric chloride was observed in the temperature range of 300 to 400 C. The graphite fluorides used for this reaction have an sp(sup 3) electronic structure and are electrical insulators. They can be made by fluorinating either carbon fibers or powder having various degrees of graphitization. Reaction is fast and spontaneous and can occur in the presence of air. The ferric chloride does not have to be predried. The products have an sp(sup 2) electronic structure and are electrical conductors. They contain first-stage FeCl3 intercalated graphite. Some of the products contain FeCl2 (center dot) 2H2O, others contain FeF3, in concentrations that depend on the intercalation condition. The graphite intercalated compounds (GIC) deintercalated slowly in air at room temperature, but deintercalated quickly and completely at 370 C. Deintercalation is accompanied by the disappearance of iron halides and the formation of rust (hematite) distributed unevenly on the fiber surface. When heated to 400 C in pure N2 (99.99 vol%), this new GIC deintercalates without losing its molecular structure. However, when the compounds are exposed to 800 C N2, in a quartz tube, they lost most of their halogen atoms and formed iron oxides (other than hematite), distributed evenly in or on the fiber.

Preparation, quantitative surface analysis, intercalation characteristics and industrial implications of low temperature expandable graphite

NASA Astrophysics Data System (ADS)

Peng, Tiefeng; Liu, Bin; Gao, Xuechao; Luo, Liqun; Sun, Hongjuan

2018-06-01

Expandable graphite is widely used as a new functional carbon material, especially as fire-retardant; however, its practical application is limited due to the high expansion temperature. In this work, preparation process of low temperature and highly expandable graphite was studied, using natural flake graphite as raw material and KMnO4/HClO4/NH4NO3 as oxidative intercalations. The structure, morphology, functional groups and thermal properties were characterized during expanding process by Fourier transform infrared spectroscopy (FTIR), Raman spectra, thermo-gravimetry differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), and scanning electron microscope (SEM). The analysis showed that by oxidation intercalation, some oxygen-containing groups were grafted on the edge and within the graphite layer. The intercalation reagent entered the graphite layer to increase the interlayer spacing. After expansion, the original flaky expandable graphite was completely transformed into worm-like expanded graphite. The order of graphite intercalation compounds (GICs) was proposed and determined to be 3 for the prepared expandable graphite, based on quantitative XRD peak analysis. Meanwhile, the detailed intercalation mechanisms were also proposed. The comprehensive investigation paved a benchmark for the industrial application of such sulfur-free expanded graphite.

Conductive Composites Made Less Expensively

NASA Technical Reports Server (NTRS)

Gaier, James R.

2005-01-01

The use of electrically conductive composite structures for electrostatic dissipation, electromagnetic interference shielding, and ground return planes could save between 30 and 90 percent of the mass of the structure, in comparison to aluminum. One strategy that has been shown to make conducting composites effectively uses intercalated graphite fiber as the reinforcement. Intercalation--the insertion of guest atoms or molecules between the graphene planes--can lower the electrical resistivity of graphite fibers by as much as a factor of 10, without sacrificing mechanical or thermal properties.

Binding modes and pathway of RHPS4 to human telomeric G-quadruplex and duplex DNA probed by all-atom molecular dynamics simulations with explicit solvent.

PubMed

Mulholland, Kelly; Siddiquei, Farzana; Wu, Chun

2017-07-19

RHPS4, a potent binder to human telomeric DNA G-quadruplex, shows high efficacy in tumor cell growth inhibition. However, it's preferential binding to DNA G-quadruplex over DNA duplex (about 10 fold) remains to be improved toward its clinical application. A high resolution structure of the single-stranded telomeric DNA G-quadruplexes, or B-DNA duplex, in complex with RHPS4 is not available yet, and the binding nature of this ligand to these DNA forms remains to be elusive. In this study, we carried out 40 μs molecular dynamics binding simulations with a free ligand to decipher the binding pathway of RHPS4 to a DNA duplex and three G-quadruplex folders (parallel, antiparallel and hybrid) of the human telomeric DNA sequence. The most stable binding mode identified for the duplex, parallel, antiparallel and hybrid G-quadruplexes is an intercalation, bottom stacking, top intercalation and bottom intercalation mode, respectively. The intercalation mode with similar binding strength to both the duplex and the G-quadruplexes, explains the lack of binding selectivity of RHPS4 to the G-quadruplex form. Therefore, a ligand modification that destabilizes the duplex intercalation mode but stabilizes the G-quadruplex intercalation mode will improve the binding selectivity toward G-quadruplex. The intercalation mode of RHPS4 to both the duplex and the antiparallel and the hybrid G-quadruplex follows a base flipping-insertion mechanism rather than an open-insertion mechanism. The groove binding, the side binding and the intercalation with flipping out of base were observed to be intermediate states before the full intercalation state with paired bases.

Multi-Step Lithiation of Tin Sulfide: An Investigation Using In Situ Electron Microscopy

DOE PAGES

Hwang, Sooyeon; Yao, Zhenpeng; Zhang, Lei; ...

2018-04-03

Two-dimensional metal sulfides have been widely explored as promising electrodes for lithium ion batteries since their two-dimensional layered structure allows lithium ions to intercalate between layers. For tin disulfide, the lithiation process proceeds via a sequence of three different types of reactions: intercalation, conversion, and alloying but the full scenario of reaction dynamics remains nebulous. In this paper, we investigate the dynamical process of the multi-step reactions using in situ electron microscopy and discover an intermediate rock-salt phase with the disordering of Li and Sn cations, after the initial 2-dimensional intercalation. The disordered cations occupy all the octahedral sites andmore » block the channels for intercalation, which alter the reaction pathways during further lithiation. Our first principles calculations of the non-equilibrium lithiation of SnS2 corroborate the energetic preference of the disordered rock-salt structure over known layered polymorphs. The in situ observations and calculations suggest a two-phase reaction nature for intercalation, disordering, and following conversion reactions. In addition, in situ de-lithiation observation confirms that the alloying reaction is reversible while the conversion reaction is not, which is consistent to the ex situ analysis. This work reveals the full lithiation characteristic of SnS2 and sheds light on the understanding of complex multistep reactions in two-dimensional materials.« less

Multi-Step Lithiation of Tin Sulfide: An Investigation Using In Situ Electron Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, Sooyeon; Yao, Zhenpeng; Zhang, Lei

Two-dimensional metal sulfides have been widely explored as promising electrodes for lithium ion batteries since their two-dimensional layered structure allows lithium ions to intercalate between layers. For tin disulfide, the lithiation process proceeds via a sequence of three different types of reactions: intercalation, conversion, and alloying but the full scenario of reaction dynamics remains nebulous. In this paper, we investigate the dynamical process of the multi-step reactions using in situ electron microscopy and discover an intermediate rock-salt phase with the disordering of Li and Sn cations, after the initial 2-dimensional intercalation. The disordered cations occupy all the octahedral sites andmore » block the channels for intercalation, which alter the reaction pathways during further lithiation. Our first principles calculations of the non-equilibrium lithiation of SnS2 corroborate the energetic preference of the disordered rock-salt structure over known layered polymorphs. The in situ observations and calculations suggest a two-phase reaction nature for intercalation, disordering, and following conversion reactions. In addition, in situ de-lithiation observation confirms that the alloying reaction is reversible while the conversion reaction is not, which is consistent to the ex situ analysis. This work reveals the full lithiation characteristic of SnS2 and sheds light on the understanding of complex multistep reactions in two-dimensional materials.« less

An intercalation-locked parallel-stranded DNA tetraplex

DOE PAGES

Tripathi, S.; Zhang, D.; Paukstelis, P. J.

2015-01-27

DNA has proved to be an excellent material for nanoscale construction because complementary DNA duplexes are programmable and structurally predictable. However, in the absence of Watson–Crick pairings, DNA can be structurally more diverse. Here, we describe the crystal structures of d(ACTCGGATGAT) and the brominated derivative, d(AC BrUCGGA BrUGAT). These oligonucleotides form parallel-stranded duplexes with a crystallographically equivalent strand, resulting in the first examples of DNA crystal structures that contains four different symmetric homo base pairs. Two of the parallel-stranded duplexes are coaxially stacked in opposite directions and locked together to form a tetraplex through intercalation of the 5'-most A–A basemore » pairs between adjacent G–G pairs in the partner duplex. The intercalation region is a new type of DNA tertiary structural motif with similarities to the i-motif. 1H– 1H nuclear magnetic resonance and native gel electrophoresis confirmed the formation of a parallel-stranded duplex in solution. Finally, we modified specific nucleotide positions and added d(GAY) motifs to oligonucleotides and were readily able to obtain similar crystals. This suggests that this parallel-stranded DNA structure may be useful in the rational design of DNA crystals and nanostructures.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferencz, Zs.; Szabados, M.; Varga, G.

2016-01-15

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

Probing the role of intercalating protein sidechains for kink formation in DNA

PubMed Central

Sandmann, Achim

2018-01-01

Protein binding can induce DNA kinks, which are for example important to enhance the specificity of the interaction and to facilitate the assembly of multi protein complexes. The respective proteins frequently exhibit amino acid sidechains that intercalate between the DNA base steps at the site of the kink. However, on a molecular level there is only little information available about the role of individual sidechains for kink formation. To unravel structural principles of protein-induced DNA kinking we have performed molecular dynamics (MD) simulations of five complexes that varied in their architecture, function, and identity of intercalated residues. Simulations were performed for the DNA complexes of wildtype proteins (Sac7d, Sox-4, CcpA, TFAM, TBP) and for mutants, in which the intercalating residues were individually or combined replaced by alanine. The work revealed that for systems with multiple intercalated residues, not all of them are necessarily required for kink formation. In some complexes (Sox-4, TBP), one of the residues proved to be essential for kink formation, whereas the second residue has only a very small effect on the magnitude of the kink. In other systems (e.g. Sac7d) each of the intercalated residues proved to be individually capable of conferring a strong kink suggesting a partially redundant role of the intercalating residues. Mutation of the key residues responsible for kinking either resulted in stable complexes with reduced kink angles or caused conformational instability as evidenced by a shift of the kink to an adjacent base step. Thus, MD simulations can help to identify the role of individual inserted residues for kinking, which is not readily apparent from an inspection of the static structures. This information might be helpful for understanding protein-DNA interactions in more detail and for designing proteins with altered DNA binding properties in the future. PMID:29432448

Probing the role of intercalating protein sidechains for kink formation in DNA.

PubMed

Sandmann, Achim; Sticht, Heinrich

2018-01-01

Protein binding can induce DNA kinks, which are for example important to enhance the specificity of the interaction and to facilitate the assembly of multi protein complexes. The respective proteins frequently exhibit amino acid sidechains that intercalate between the DNA base steps at the site of the kink. However, on a molecular level there is only little information available about the role of individual sidechains for kink formation. To unravel structural principles of protein-induced DNA kinking we have performed molecular dynamics (MD) simulations of five complexes that varied in their architecture, function, and identity of intercalated residues. Simulations were performed for the DNA complexes of wildtype proteins (Sac7d, Sox-4, CcpA, TFAM, TBP) and for mutants, in which the intercalating residues were individually or combined replaced by alanine. The work revealed that for systems with multiple intercalated residues, not all of them are necessarily required for kink formation. In some complexes (Sox-4, TBP), one of the residues proved to be essential for kink formation, whereas the second residue has only a very small effect on the magnitude of the kink. In other systems (e.g. Sac7d) each of the intercalated residues proved to be individually capable of conferring a strong kink suggesting a partially redundant role of the intercalating residues. Mutation of the key residues responsible for kinking either resulted in stable complexes with reduced kink angles or caused conformational instability as evidenced by a shift of the kink to an adjacent base step. Thus, MD simulations can help to identify the role of individual inserted residues for kinking, which is not readily apparent from an inspection of the static structures. This information might be helpful for understanding protein-DNA interactions in more detail and for designing proteins with altered DNA binding properties in the future.

In situ oligomerization of 2-(thiophen-3-yl)acetate intercalated into Zn{sub 2}Al layered double hydroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tronto, Jairo, E-mail: jairotronto@ufv.br; Pinto, Frederico G.; Costa, Liovando M. da

2015-01-15

A layered double hydroxide (LDH) with cation composition Zn{sub 2}Al was intercalated with 2-(thiophen-3-yl)acetate (3-TA) monomers. To achieve in situ polymerization and/or oligomerization of the intercalated monomers, soft thermal treatments were carried out, and subsequent hybrid LDH materials were analyzed by means of several characterization techniques using powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), {sup 13}C CP–MAS nuclear magnetic resonance (NMR), electron spin resonance (EPR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP–OES), and elemental analysis. PXRD analysis suggested that the intercalated monomers formed a bilayer. Thermalmore » treatment of the hybrid LDH assembly above 120 °C provokes partially the breakdown of the layered structure, generating the phase zincite. EPR results indicated that vicinal monomers (oligomerization) were bound to each other after hydrothermal or thermal treatment, leading to a polaron response characteristic of electron conductivity localized on a restricted number of thiophene-based monomer segments. Localized unpaired electrons exist in the material and interact with the {sup 27}Al nuclei of the LDH layers by superhyperfine coupling. These unpaired electrons also interact with the surface of ZnO (O{sup 2−} vacancies), formed during the thermal treatments. - Graphical abstract: We synthesized a layered double hydroxide (LDH) with cation composition Zn{sub 2}Al, intercalated with 2-(thiophen-3-yl)acetate (3-TA) monomers, by coprecipitation at constant pH. We thermally treated the material, to achieve in situ polymerization and/or oligomerization of the intercalated monomers. - Highlights: • A Zn{sub 2}Al–LDH was intercalated with 2-(thiophen-3-yl)acetate monomers. • To achieve in situ oligomerization of the monomers, thermal treatments were made. • Thermal treatment above 120 °C causes partially breakdown of the LDH structure. • ESR results indicated a polaron response characteristic of electron conductivity.« less

Structural analysis of nanocomposites based on HDPE/EPDM blends.

PubMed

Zitzumbo, Roberto; Alonso, Sergio; Avalos, Felipe; Ortiz, José C; López-Manchado, Miguel A; Arroyo, Miguel

2006-02-01

Intercalated and exfoliated nanocomposites based on HDPE and EPDM blends with an organoclay have been obtained through the addition of EPDM-g-MA as a compatibilizer. The combined effect of clay and EPDM-g-MA on the rheological behaviour is very noticeable with a sensible increase in viscosity which suggests the formation of a structural net of percolation induced by the presence of intercalated and exfoliated silicate layer. As deduced from rheological studies, a morphology based on nanostructured micro-domains dispersed in HDPE continuous phase is proposed for EPDM/HDPE blend nanocomposites. XRD and SEM analysis suggest that two different transport phenomena take simultaneously place during the intercalation process in the melt. One due to diffusion of HDPE chains into the tactoid and the other to diffusion of EPDM-g-MA into the silicate galleries.

Investigation de l'anisotropie du gap supraconducteur dans les composes Ba(Fe(1-x)Co(x))2As2, Ba(1-x)K(x)Fe2As2, LiFeAs et Fe1-deltaTe(1-x)Se(x)

NASA Astrophysics Data System (ADS)

Reid, Jean-Philippe

ommaire La structure du gap supraconducteur et sa modulation sont intimement liees au potentiel d'interaction responsable de l'appariement des electrons d'un supraconducteur. Ainsi, l'etude de la structure du gap-SC et de sa modulation permettent de faire la lumiere sur la nature du mecanisme d'appariement des electrons. A cet egard, les resultats experimentaux des supraconducteurs a base de fer ne cadrent pas dans un seul ensemble, ce qui est en opposition au gap-SC universel des cuprates. Dans ce qui suit, nous presenterons une etude systematique du gap-SC pour plusieurs pnictides. En effet, en utilisant la conductivite thermique, une sonde directionnelle du gap-SC, nous avons ete en mesure de reveler la structure du gap-SC pour les composes suivants : Ba1-xKxFe 2As2, Ba(Fe1-xCo x)2As2, LiFeAs et Fe1-deltaTe 1-xSex. L'etude de ces quatre composes, de trois differentes familles structurales, a pu etablir un tableau partiel mais tres exhaustif de la structure du gap-SC de pnictides. En effet, tel qu'illustre dans cette these, ces quatre composes ne possedent aucun noeud dans leur structure du gap-SC a dopage optimal. Toutefois, a une concentration differente de celle optimale pour les composes K-Ba122 et Co-Ba122, des noeuds apparaissent sur la surface de Fermi, aux extremites 'du dome supraconducteur. Ceci suggere fortement que, pour ces composes, la presence de noeuds sur la surface de Fermi est nuisible a la phase supraconductrice. Mots-cles: Supraconducteurs a base de fer, Pnictides, Structure du gap supraconducteur, Conductivite thermique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia Shengjie; Ni Zheming; Xu Qian

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

1,8-Naphthalimide: A Potent DNA Intercalator and Target for Cancer Therapy.

PubMed

Tandon, Runjhun; Luxami, Vijay; Kaur, Harsovin; Tandon, Nitin; Paul, Kamaldeep

2017-10-01

The poor pharmacokinetics, side effects and particularly the rapid emergence of drug resistance compromise the efficiency of clinically used anticancer drugs. Therefore, the discovery of novel and effective drugs is still an extremely primary mission. Naphthalimide family is one of the highly active anticancer drug based upon effective intercalator with DNA. In this article, we review the discovery and development of 1,8-naphthalimide moiety, and, especially, pay much attention to the structural modifications and structure activity relationships. The review demonstrates how modulation of the moiety affecting naphthalimide compound for DNA binding that is achieved to afford a profile of antitumor activity. The DNA binding of imide and ring substitution at naphthalimide, bisnaphthalimide, naphthalimide-metal complexes is achieved by molecular recognition through intercalation mode. Thus, this synthetic/natural small molecule can act as a drug when activation or inhibition of DNA function, is required to cure or control the cancer disease. The present study is a review of the advances in 1,8-naphthalimide-related research, with a focus on how such derivatives are intercalated into DNA for their anticancer activities. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-rate capability of three-dimensionally ordered macroporous T-Nb2O5 through Li+ intercalation pseudocapacitance

NASA Astrophysics Data System (ADS)

Lou, Shuaifeng; Cheng, Xinqun; Wang, Long; Gao, Jinlong; Li, Qin; Ma, Yulin; Gao, Yunzhi; Zuo, Pengjian; Du, Chunyu; Yin, Geping

2017-09-01

Orthorhombic Niobium oxide (T-Nb2O5) has been regarded as a promising anode material for high-rate lithium ion batteries (LIBs) due to its potential to operate at high rates with improved safety and high theoretical capacity of 200 mA h g-1. Herein, three-dimensionally ordered macroporous (3DOM) T-Nb2O5, with mesoporous hierarchical structure, was firstly prepared by a simple approach employing self-assembly polystyrene (PS) microspheres as hard templates. The obtained T-Nb2O5 anode material presents obvious and highly-efficiency pseudocapacitive Li+ intercalation behaviour, which plays a dominant role in the kinetics of electrode process. As a result, rapid Li+ intercalation/de-intercalation are achieved, leading to excellent rate capability and long cycle life. The 3DOM T-Nb2O5 shows a remarkable high capacity of 106 and 77 mA h g-1 at the rate of 20C and 50C. The work presented herein holds great promise for future design of material structure, and demonstrates the great potential of T-Nb2O5 as a practical high-rate anode material for LIBs.

Ferric chloride graphite intercalation compounds prepared from graphite fluoride

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1994-01-01

The reaction between graphite fluoride and ferric chloride was observed in the temperature range of 300 to 400 C. The graphite fluorides used for this reaction have an sp3 electronic structure and are electrical insulators. They can be made by fluorinating either carbon fibers or powder having various degrees of graphitization. Reaction is fast and spontaneous and can occur in the presence of air. The ferric chloride does not have to be predried. The products have an sp2 electronic structure and are electrical conductors. They contain first stage FeCl3 intercalated graphite. Some of the products contain FeCl2*2H2O, others contain FeF3 in concentrations that depend on the intercalation condition. The graphite intercalated compounds (GIC) deintercalated slowly in air at room temperature, but deintercalated quickly and completely at 370 C. Deintercalation is accompanied by the disappearing of iron halides and the formation of rust (hematite) distributed unevenly on the fiber surface. When heated to 400 C in pure N2 (99.99 vol %), this new GIC deintercalates without losing its molecular structure. However, when the compounds are heated to 800 C in quartz tube, they lost most of its halogen atoms and formed iron oxides (other than hematite), distributed evenly in or on the fiber. This iron-oxide-covered fiber may be useful in making carbon-fiber/ceramic-matrix composites with strong bonding at the fiber-ceramic interface.

Bioinspired artificial photonic nanoarchitecture using the elytron of the beetle Trigonophorus rothschildi varians as a ‘blueprint’

PubMed Central

Biró, L. P.; Kertész, K.; Horváth, E.; Márk, G. I.; Molnár, G.; Vértesy, Z.; Tsai, J.-F.; Kun, A.; Bálint, Zs.; Vigneron, J. P.

2010-01-01

An unusual, intercalated photonic nanoarchitecture was discovered in the elytra of Taiwanese Trigonophorus rothschildi varians beetles. It consists of a multilayer structure intercalated with a random distribution of cylindrical holes normal to the plane of the multilayer. The nanoarchitectures were characterized structurally by scanning electron microscopy and optically by normal incidence, integrated and goniometric reflectance measurements. They exhibit an unsaturated specular and saturated non-specular component of the reflected light. Bioinspired, artificial nanoarchitectures of similar structure and with similar properties were realized by drilling holes of submicron size in a multilayer structure, showing that such photonic nanoarchitectures of biological origin may constitute valuable blueprints for artificial photonic materials. PMID:19933221

The role of ionic liquid electrolyte in an aluminum–graphite electrochemical cell

DOE PAGES

Agiorgousis, Michael L.; Sun, Yi -Yang; Zhang, Shengbai

2017-02-17

Using first-principles calculations and molecular dynamics simulation, we study the working mechanism in an aluminum–graphite electrochemical cell, which was recently reported to exhibit attractive performance. We exclude the possibility of Al 3+ cation intercalation into graphite as in standard Li-ion batteries. Instead, we show that the AlCl 4 – anion intercalation mechanism is thermodynamically feasible. By including the ionic liquid electrolyte in the overall redox reaction, we are able to reproduce the high voltage observed in experiment. The active involvement of electrolyte in the reaction suggests that the evaluation of energy density needs to take the electrolyte into consideration. Here,more » our proposed structural model is consistent with the new peaks appearing in X-ray diffraction from the intercalation compound. The high rate capability is explained by the ultralow diffusion barriers of the AlCl 4 intercalant. With the clarified working mechanism, it becomes clear that the high voltage of the Al–graphite cell is a result of the thermodynamic instability of the AlCl 4-intercalated graphite.« less

Localized concentration reversal of lithium during intercalation into nanoparticles

DOE PAGES

Zhang, Wei; Yu, Hui -Chia; Wu, Lijun; ...

2018-01-12

Nanoparticulate electrodes, such as Li xFePO 4, have unique advantages over their microparticulate counterparts for the applications in Li-ion batteries because of the shortened diffusion path and access to nonequilibrium routes for fast Li incorporation, thus radically boosting power density of the electrodes. However, how Li intercalation occurs locally in a single nanoparticle of such materials remains unresolved because real-time observation at such a fine scale is still lacking. We report visualization of local Li intercalation via solid-solution transformation in individual Li xFePO 4 nanoparticles, enabled by probing sub-angstrom changes in the lattice spacing in situ. The real-time observation revealsmore » inhomogeneous intercalation, accompanied with an unexpected reversal of Li concentration at the nanometer scale. The origin of the reversal phenomenon is elucidated through phase-field simulations, and it is attributed to the presence of structurally different regions that have distinct chemical potential functions. Furthermore, the findings from this study provide a new perspective on the local intercalation dynamics in battery electrodes.« less

Collecting Duct Intercalated Cell Function and Regulation

PubMed Central

Roy, Ankita; Al-bataineh, Mohammad M.

2015-01-01

Intercalated cells are kidney tubule epithelial cells with important roles in the regulation of acid-base homeostasis. However, in recent years the understanding of the function of the intercalated cell has become greatly enhanced and has shaped a new model for how the distal segments of the kidney tubule integrate salt and water reabsorption, potassium homeostasis, and acid-base status. These cells appear in the late distal convoluted tubule or in the connecting segment, depending on the species. They are most abundant in the collecting duct, where they can be detected all the way from the cortex to the initial part of the inner medulla. Intercalated cells are interspersed among the more numerous segment-specific principal cells. There are three types of intercalated cells, each having distinct structures and expressing different ensembles of transport proteins that translate into very different functions in the processing of the urine. This review includes recent findings on how intercalated cells regulate their intracellular milieu and contribute to acid-base regulation and sodium, chloride, and potassium homeostasis, thus highlighting their potential role as targets for the treatment of hypertension. Their novel regulation by paracrine signals in the collecting duct is also discussed. Finally, this article addresses their role as part of the innate immune system of the kidney tubule. PMID:25632105

Atomistic Conversion Reaction Mechanism of WO 3 in Secondary Ion Batteries of Li, Na, and Ca

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Yang; Gu, Meng; Xiao, Haiyan

2016-04-13

Reversible insertion and extraction of ionic species into a host lattice governs the basic operating principle for both rechargeable battery (such as lithium batteries) and electrochromic devices (such as ANA Boeing 787-8 Dreamliner electrochromic window). Intercalation and/or conversion are two fundamental chemical processes for some materials in response to the ion insertion. The interplay between these two chemical processes has never been established. It is speculated that the conversion reaction is initiated by ion intercalation. However, experimental evidence of intercalation and subsequent conversion remains unexplored. Here, using in situ HRTEM and spectroscopy, we captured the atomistic conversion reaction processes duringmore » lithium, sodium and calcium ion insertion into tungsten trioxide (WO3) single crystal model electrodes. An intercalation step right prior to conversion is explicitly revealed at atomic scale for the first time for these three ion species. Combining nanoscale diffraction and ab initio molecular dynamics simulations, it is found that, beyond intercalation, the inserted ion-oxygen bonding formation destabilized the transition-metal framework which gradually shrunk, distorted and finally collapsed to a pseudo-amorphous structure. This study provides a full atomistic picture on the transition from intercalation to conversion, which is of essential for material applications in both secondary ion batteries and electrochromic devices.« less

Effect of humidity and water intercalation on the tribological behavior of graphene and graphene oxide.

PubMed

Arif, Taib; Colas, Guillaume; Filleter, Tobin

2018-06-12

In this work, the effect of humidity and water intercalation on the friction and wear behavior of few-layers of graphene and graphene oxide (GO) was studied using friction force microscopy. Thickness measurements demonstrated significant water intercalation within GO affecting its surface topography (roughness and protrusions), whereas negligible water intercalation of graphene was observed. It was found that water intercalation in GO contributed to wearing of layers at a relative humidity as low as ~30%. The influence of surface wettability and water adsorption was also studied by comparing the sliding behavior of SiO2/GO, SiO2/Graphene, and SiO2/SiO2 interfaces. Friction for the SiO2/GO interface increased with relative humidity due to water intercalation and condensation of water. In contrast, it was observed that adsorption of water molecules lubricated the SiO2/SiO2 interface due to easy shearing of water on the hydrophobic surface, particularly once the adsorbed water layers had transitioned from "ice-like water" to "liquid-like water" structures. Lastly, an opposite friction trend was observed for the graphene/SiO2 interface with water molecules failing to lubricate the interface as compared to the dry graphene/SiO2 contact.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Yinghui; Lii-Rosales, Ann; Kim, Minsung

Here, we show that 3 metals – Dy, Ru, and Cu – can form multilayer intercalated (encapsulated) islands at the graphite (0001) surface if 2 specific conditions are met: Defects are introduced on the graphite terraces to act as entry portals, and the metal deposition temperature is well above ambient. Focusing on Dy as a prototype, we show that surface encapsulation is much different than bulk intercalation, because the encapsulated metal takes the form of bulk-like rafts of multilayer Dy, rather than the dilute, single-layer structure known for the bulk compound. Carbon-covered metallic rafts even form for relatively unreactive metalsmore » (Ru and Cu) which have no known bulk intercalation compound.« less

Intercalation Pseudocapacitance of Exfoliated Molybdenum Disulfide for Ultrafast Energy Storage

DOE PAGES

Yoo, Hyun Deog; Li, Yifei; Liang, Yanliang; ...

2016-05-23

In this study, we report intercalation pseudocapacitance of 250 F g -1 for exfoliated molybdenum disulfide (MoS 2) in non-aqueous electrolytes that contain lithium ions. The exfoliated MoS 2 shows surface-limited reaction kinetics with high rate capability up to 3 min of charge or discharge. The intercalation pseudocapacitance originates from the extremely fast kinetics due to the enhanced ionic and electronic transport enabled by the slightly expanded layer structure as well as the metallic 1T-phase. The exfoliated MoS 2 could be also used in a Li-Mg-ion hybrid capacitor, which shows full cell specific capacitance of 240 F g -1.

First-principles study of Ti intercalation between graphene and Au surface

NASA Astrophysics Data System (ADS)

Kaneko, T.; Imamura, H.

2011-06-01

We investigate the effects of Ti intercalation between graphene and Au surface on binding energy and charge doping by using the first-principles calculations. We show that the largest binding energy is realized by the intercalation of single mono-layer of Ti. We also show that electronic structure is very sensitive to the arrangement of metal atoms at the interface. If the composition of the interface layer is Ti0.33Au0.67 and the Ti is located at the top site, the Fermi level lies closely at the Dirac point, i.e., the Dirac cone of the ideal free-standing graphene is recovered.

Intercalation of P atoms in Fullerene-like CP x

NASA Astrophysics Data System (ADS)

Gueorguiev, G. K.; Czigány, Zs.; Furlan, A.; Stafström, S.; Hultman, L.

2011-01-01

The energy cost for P atom intercalation and corresponding structural implications during formation of Fullerene-like Phosphorus carbide (FL-CPx) were evaluated within the framework of Density Functional Theory. Single P atom interstitial defects in FL-CPx are energetically feasible and exhibit energy cost of 0.93-1.21 eV, which is comparable to the energy cost for experimentally confirmed tetragon defects and dangling bonds in CPx. A single P atom intercalation event in FL-CPx can increase the inter-sheet distance from 3.39-3.62 Å to 5.81-7.04 Å. These theoretical results are corroborated by Selected Area Electron Diffraction characterization of FL-CPx samples.

Tuning Fullerene Intercalation in a Poly (thiophene) derivative by Controlling the Polymer Degree of Self-Organisation

NASA Astrophysics Data System (ADS)

Paternò, G. M.; Skoda, M. W. A.; Dalgliesh, Robert; Cacialli, F.; Sakai, V. García

2016-10-01

Controlling the nanoscale arrangement in polymer-fullerene organic solar cells is of paramount importance to boost the performance of such promising class of photovoltaic diodes. In this work, we use a pseudo-bilayer system made of poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), to acquire a more complete understanding of the diffusion and intercalation of the fullerene-derivative within the polymer layer. By exploiting morphological and structural characterisation techniques, we observe that if we increase the film solidification time the polymer develops a higher crystalline order, and, as a result, it does not allow fullerene molecules to intercalate between the polymer side-chains. Gaining insight into the detailed fullerene intercalation mechanism is important for the development of organic photovoltaic diodes (PVDs).

Tuning Fullerene Intercalation in a Poly (thiophene) derivative by Controlling the Polymer Degree of Self-Organisation.

PubMed

Paternò, G M; Skoda, M W A; Dalgliesh, Robert; Cacialli, F; Sakai, V García

2016-10-04

Controlling the nanoscale arrangement in polymer-fullerene organic solar cells is of paramount importance to boost the performance of such promising class of photovoltaic diodes. In this work, we use a pseudo-bilayer system made of poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM), to acquire a more complete understanding of the diffusion and intercalation of the fullerene-derivative within the polymer layer. By exploiting morphological and structural characterisation techniques, we observe that if we increase the film solidification time the polymer develops a higher crystalline order, and, as a result, it does not allow fullerene molecules to intercalate between the polymer side-chains. Gaining insight into the detailed fullerene intercalation mechanism is important for the development of organic photovoltaic diodes (PVDs).

Tuning Fullerene Intercalation in a Poly (thiophene) derivative by Controlling the Polymer Degree of Self-Organisation

PubMed Central

Paternò, G. M.; Skoda, M. W. A.; Dalgliesh, Robert; Cacialli, F.; Sakai, V. García

2016-01-01

Controlling the nanoscale arrangement in polymer-fullerene organic solar cells is of paramount importance to boost the performance of such promising class of photovoltaic diodes. In this work, we use a pseudo-bilayer system made of poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), to acquire a more complete understanding of the diffusion and intercalation of the fullerene-derivative within the polymer layer. By exploiting morphological and structural characterisation techniques, we observe that if we increase the film solidification time the polymer develops a higher crystalline order, and, as a result, it does not allow fullerene molecules to intercalate between the polymer side-chains. Gaining insight into the detailed fullerene intercalation mechanism is important for the development of organic photovoltaic diodes (PVDs). PMID:27698410

Metal complexes as DNA intercalators.

PubMed

Liu, Hong-Ke; Sadler, Peter J

2011-05-17

DNA has a strong affinity for many heterocyclic aromatic dyes, such as acridine and its derivatives. Lerman in 1961 first proposed intercalation as the source of this affinity, and this mode of DNA binding has since attracted considerable research scrutiny. Organic intercalators can inhibit nucleic acid synthesis in vivo, and they are now common anticancer drugs in clinical therapy. The covalent attachment of organic intercalators to transition metal coordination complexes, yielding metallointercalators, can lead to novel DNA interactions that influence biological activity. Metal complexes with σ-bonded aromatic side arms can act as dual-function complexes: they bind to DNA both by metal coordination and through intercalation of the attached aromatic ligand. These aromatic side arms introduce new modes of DNA binding, involving mutual interactions of functional groups held in close proximity. The biological activity of both cis- and trans-diamine Pt(II) complexes is dramatically enhanced by the addition of σ-bonded intercalators. We have explored a new class of organometallic "piano-stool" Ru(II) and Os(II) arene anticancer complexes of the type [(η(6)-arene)Ru/Os(XY)Cl](+). Here XY is, for example, ethylenediamine (en), and the arene ligand can take many forms, including tetrahydroanthracene, biphenyl, or p-cymene. Arene-nucleobase stacking interactions can have a significant influence on both the kinetics and thermodynamics of DNA binding. In particular, the cytotoxic activity, conformational distortions, recognition by DNA-binding proteins, and repair mechanisms are dependent on the arene. A major difficulty in developing anticancer drugs is cross-resistance, a phenomenon whereby a cell that is resistant to one drug is also resistant to another drug in the same class. These new complexes are non-cross-resistant with cisplatin towards cancer cells: they constitute a new class of anticancer agents, with a mechanism of action that differs from the anticancer drug cisplatin and its analogs. The Ru-arene complexes with dual functions are more potent towards cancer cells than their nonintercalating analogs. In this Account, we focus on recent studies of dual-function organometallic Ru(II)- and Os(II)-arene complexes and the methods used to detect arene-DNA intercalation. We relate these interactions to the mechanism of anticancer activity and to structure-activity relationships. The interactions between these complexes and DNA show close similarities to those of covalent polycyclic aromatic carcinogens, especially to N7-alkylating intercalation compounds. However, Ru-arene complexes exhibit some new features. Classical intercalation and base extrusion next to the metallated base is observed for {(η(6)-biphenyl)Ru(ethylenediamine)}(2+) adducts of a 14-mer duplex, while penetrating arene intercalation occurs for adducts of the nonaromatic bulky intercalator {(η(6)-tetrahydroanthracene)Ru(ethylenediamine)}(2+) with a 6-mer duplex. The introduction of dual-function Ru-arene complexes introduces new mechanisms of antitumor activity, novel mechanisms for attack on DNA, and new concepts for developing structure- activity relationships. We hope this discussion will stimulate thoughtful and focused research on the design of anticancer chemotherapeutic agents using these unique approaches.

Comparative analysis of topoisomerase IB inhibition and DNA intercalation by flavonoids and similar compounds: structural determinates of activity

PubMed Central

2004-01-01

Flavonoids and other polyphenolic compounds have been shown to inhibit human topoisomerase IB (topo I) through both inhibition of relaxation activity and through stabilization of the cleavable complex (poisoning). Some flavonoids have also been shown to intercalate DNA, and an association of topoisomerase inhibition with intercalation has been noted. We surveyed 34 polyphenolic compounds, primarily flavonoid glycones and aglycones, for their ability to inhibit topo I and to intercalate DNA using an in vitro gel electrophoresis method. We show that the most potent topo I poisons are the flavones and flavonols, and that these generally, but not always, are found to be DNA intercalators. There was no clear correlation, however, of topo-I-poisoning activity with the degree of DNA unwinding. Surprisingly, both DNA intercalation and topo I poisoning were shown to occur with some flavone glycones, including the C-glycosylflavone orientin. Inhibition of relaxation activity by flavonoids was found to be difficult to quantify and was most likely to be due to non-specific inhibition through flavonoid aggregation. As part of a structure–activity analysis, we also investigated the acid–base chemistry of flavonoids and determined that many flavonoids show acid–base activity with a pKa in the physiological pH region. For this reason, subtle pH changes can have significant effects on solution activity of flavonoids and their concomitant biological activity. In addition, these effects may be complicated by pH-dependent aggregation and oxidative degradation. Finally, we develop a simple model for the intercalation of flavonoids into DNA and discuss possible consequences of intercalation and topoisomerase inhibition on a number of cellular processes. PMID:15312049

HRTEM and neutron diffraction study of Li{sub x}Mo{sub 5}O{sub 17}: From the ribbon (x=5) structure to the rock salt (x=12) structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lebedev, O.I.; Caignaert, V.; Raveau, B.

2011-04-15

Structure determination of the fully intercalated phase Li{sub 12}Mo{sub 5}O{sub 17} and of the deintercalated oxide Li{sub 5}Mo{sub 5}O{sub 17} has been carried out by electron microscopy and neutron powder diffraction. The reversible topotactic transformation between the ordered rock salt structure of the former and the ribbon structure of the latter (closely related to that of Li{sub 4}Mo{sub 5}O{sub 17}) is explained on the following basis: both structures can be described as strips built up as an assembly of infinite ribbons of MoO{sub 6} octahedra that are five octahedra thick, and that differ by slight displacements of the octahedral ribbons.more » We show that the electrochemical behavior of the Li{sub x}Mo{sub 5}O{sub 17} system is based on two sorts of Li{sup +} sites; those that are located within the strips between the ribbons, and those that are located at the border of the strips. The high rate of Li intercalation in this oxide and its reversibility are discussed in terms of its peculiar structure. -- Graphical abstract: Structure determination of the fully intercalated phase Li{sub 12}Mo{sub 5}O{sub 17} and of the deintercalated oxide Li{sub 5}Mo{sub 5}O{sub 17} has been carried out by electron microscopy and neutron powder diffraction. The reversible topotactic transformation between the ordered rock salt structure of the former and the ribbon structure of the latter is explained on the following basis: both structures can be described as strips built up as an assembly of infinite ribbons of MoO{sub 6} octahedra that are five octahedra thick, and that differ by slight displacements of the octahedral ribbons. We show that the electrochemical behavior of the Li{sub x}Mo{sub 5}O{sub 17} system is based on two sorts of Li{sup +} sites; those that are located within the strips between the ribbons, and those that are located at the border of the strips. The high rate of Li intercalation in this oxide and its reversibility are discussed in terms of its peculiar structure. Research highlights: {yields} Electron microscopy and neutron powder diffraction structure determination {yields} We have explained the reversible topotactic transformation between an ordered rock salt structure and a ribbon structure {yields} We show that the electrochemical behavior of the Li{sub x}Mo{sub 5}O{sub 17} system is based on two sorts of Li{sup +} sites {yields} The high rate of Li intercalation in this oxide and its reversibility are discussed in terms of its peculiar structure.« less

Electronic and structural properties of B i2S e3:Cu

NASA Astrophysics Data System (ADS)

Sobczak, Kamil; Strak, Pawel; Kempisty, Pawel; Wolos, Agnieszka; Hruban, Andrzej; Materna, Andrzej; Borysiuk, Jolanta

2018-04-01

Electronic and structural properties of B i2S e3 and its extension to copper doped B i2S e3:Cu were studied using combined ab initio simulations and transmission electron microscopy based techniques, including electron energy loss spectroscopy, energy filtered transmission electron microscopy, and energy dispersive x-ray spectroscopy. The stability of the mixed phases was investigated for substitutional and intercalation changes of basic B i2S e3 structure. Four systems were compared: B i2S e3 , structures obtaining by Cu intercalation of the van der Waals gap, by substitution of Bi by Cu in quintuple layers, and C u2Se . The structures were identified and their electronic properties were obtained. Transmission electron microscopy measurements of B i2S e3 and the B i2S e3:Cu system identified the first structure as uniform and the second as composite, consisting of a nonuniform lower-Cu-content matrix and randomly distributed high-Cu-concentration precipitates. Critical comparison of the ab initio and experimental data identified the matrix as having a B i2S e3 dominant part with randomly distributed Cu-intercalated regions having 1Cu-B i2S e3 structure. The precipitates were determined to have 3Cu-B i2S e3 structure.

Hydroxy double salts loaded with bioactive ions: Synthesis, intercalation mechanisms, and functional performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaassis, Abdessamad Y.A.; Xu, Si-Min; Guan, Shanyue

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 [Co{sub 1.2}Zn{sub 3.8}(OH){sub 8}](NO{sub 3}){sub 2}·2H{sub 2}O (CoZn-NO{sub 3}), [Ni{sub 2}Zn{sub 3}(OH){sub 8}](NO{sub 3}){sub 2}·2H{sub 2}O (NiZn-NO{sub 3}) and [Zn{sub 5}(OH){sub 8}](NO{sub 3}){sub 2}·2H{sub 2}O (Zn-NO{sub 3}). It proved possible to intercalate diclofenac and naproxen into all three HDSs. In contrast, Val could be intercalated into CoZn-NO{sub 3} but when it was reacted with Zn-NO{sub 3} the HDS structure was destroyed, and the product comprised ZnO. Successful intercalation was verifiedmore » 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-NO{sub 3} and Zn-NO{sub 3} is mechanistically complex, with a number of intermediate phases observed. In contrast, the intercalation of all three guests into NiZn-NO{sub 3} and of Val into CoZn-NO{sub 3} 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. - Graphical abstract: Seven new drug intercalates of hydroxy double salts (HDSs) have been prepared and characterised. The intercalation mechanisms have been explored, and the drug release properties of the HDS/drug composites quantified. Display Omitted.« less

Highly Conducting Graphite Epoxy Composite Demonstrated

NASA Technical Reports Server (NTRS)

Gaier, James R.

1999-01-01

Weight savings as high as 80 percent could be achieved if graphite polymer composites could replace aluminum in structures such as electromagnetic interference shielding covers and grounding planes. This could result in significant cost savings, especially for the mobile electronics found in spacecraft, aircraft, automobiles, and hand-held consumer electronics. However, such composites had not yet been fabricated with conductivity sufficient to enable these applications. To address this lack, a partnership of the NASA Lewis Research Center, Manchester College, and Applied Sciences, Inc., fabricated nonmetallic composites with unprecedented electrical conductivity. For these composites, heat-treated, vapor-grown graphite fibers were selected which have a resistivity of about 80 mW-cm, more than 20 times more conductive than typical carbon fibers. These fibers were then intercalated with iodine bromide (IBr). Intercalation is the insertion of guest atoms or molecules between the carbon planes of the graphite fibers. Since the carbon planes are not highly distorted in the process, intercalation has little effect on mechanical and thermal properties. Intercalation does, however, lower the carbon fiber resistivity to less than 10 mW-cm, which is comparable to that of metal fibers. Scaleup of the reaction was required since the initial intercalation experiments would be carried out on 20-mg quantities of fibers, and tens of grams of intercalated fibers would be needed to fabricate even small demonstration composites. The reaction was first optimized through a time and temperature study that yielded fibers with a resistivity of 8.7 2 mW-cm when exposed to IBr vapor at 114 C for 24 hours. Stability studies indicated that the intercalated fibers rapidly lost their conductivity when exposed to temperatures as low as 40 C in air. They were not, however, susceptible to degradation by water vapor in the manner of most graphite intercalation compounds. The 1000-fold scaleup experiments concluded that 114 C was near the optimum temperature, but that the intercalation time needed to be lengthened by a factor of 3.

Complex Stoichiometry reordering of PTCDA on Ag(111) upon K Intercalation

NASA Astrophysics Data System (ADS)

Brivio, G. P.; Baby, A.; Zwick, C.; Gruenewald, M.; Forker, R.; Fritz, T.; Fratesi, G.; Hofmann, O. T.; Zojer, E.

Alkali metal atoms are a simple yet efficient n-type dopant of organic semiconductors. However, the molecular crystal structures need be controlled and well understood in order to optimize the electronic properties (charge carrier density and mobility) of the target material. Here, we report that potassium intercalation into PTCDA monolayer domains on a Ag(111) substrate induces distinct stoichiometry-dependent structural reordering processes, resulting in highly ordered and large KxPTCDA domains. The emerging structures are analyzed by low temperature scanning tunneling microscopy (STM), scanning tunneling hydrogen microscopy (STHM), and low-energy electron diffraction (LEED) as a function of the stoichiometry and by density functional theory (DFT) calculations. Large stable monolayer domains are found for x=2,4. The epitaxy types for all intercalated stages are determined as point-on-line. The K atoms adsorb in the vicinity of the oxygen atoms of the PTCDA molecules, and their positions are determined with sub-Angstrom precision. This is a crucial prerequisite for the prospective assessment of the electronic properties of such composite films, as they depend on the mutual alignment between donor atoms and acceptor molecules.

Intercalation of cellulase enzyme into a hydrotalcite layer structure

NASA Astrophysics Data System (ADS)

Zou, N.; Plank, J.

2015-01-01

A new inorganic-organic hybrid material whereby cellulase enzyme is incorporated into a hydrotalcite type layered double hydroxide (LDH) structure is reported. The Mg2Al-cellulase-LDH was synthesized via co-precipitation from Mg/Al nitrate at pH=9.6. Characterization was performed using X-ray powder diffraction (XRD), small angle X-ray scattering (SAXS), elemental analysis, infrared spectroscopy (IR) and thermogravimetry (TG). From XRD and SAXS measurements, a d-value of ~5.0 nm was identified for the basal spacing of the Mg2Al-cellulase-LDH. Consequently, the cellulase enzyme (hydrodynamic diameter ~6.6 nm) attains a slightly compressed conformation when intercalated. Formation of the LDH hybrid was also confirmed via scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Mg2Al-cellulase-LDH phases appear as ~20 nm thin foils which are intergrown to flower-like aggregates. Activity of the enzyme was retained after deintercalation from the Mg2Al-LDH framework using anion exchange. Accordingly, cellulase is not denatured during the intercalation process, and LDH presents a suitable host structure for time-controlled release of the biomolecule.

Metallization and superconductivity in Ca-intercalated bilayer MoS2

NASA Astrophysics Data System (ADS)

Szczȱśniak, R.; Durajski, A. P.; Jarosik, M. W.

2017-12-01

A two-dimensional molybdenum disulfide (MoS2) has attracted significant interest recently due to its outstanding physical, chemical and optoelectronic properties. In this paper, using the first-principles calculations, the dynamical stability, electronic structure and superconducting properties of Ca-intercalated bilayer MoS2 are investigated. The calculated electron-phonon coupling constant implies that the stable form of investigated system is a strong-coupling superconductor (λ = 1.05) with a low value of critical temperature (TC = 13.3 K). Moreover, results obtained within the framework of the isotropic Migdal-Eliashberg formalism proved that Ca-intercalated bilayer MoS2 exhibits behavior that goes beyond the scope of the conventional BCS theory.

Intercalation of paracetamol into the hydrotalcite-like host

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kovanda, Frantisek, E-mail: Frantisek.Kovanda@vscht.cz; Maryskova, Zuzana; Kovar, Petr

2011-12-15

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 Degree-Sign 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 nearmore » 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. - Graphical abstract: Molecular simulations showed disordered arrangement of paracetamol molecules in the interlayer; most of the interlayer water molecules are located near the hydroxide sheets. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Paracetamol was intercalated in Mg-Al hydrotalcite-like host by rehydration/reconstruction procedure. Black-Right-Pointing-Pointer Paracetamol phenolic groups interact with positively charged sites in hydroxide sheets. Black-Right-Pointing-Pointer Molecular simulations showed disordered arrangement of guest molecules in the interlayer. Black-Right-Pointing-Pointer Slower release of paracetamol intercalated in the hydrotalcite-like host was observed.« less

Crystal structure of a four-stranded intercalated DNA: d(C4)

NASA Technical Reports Server (NTRS)

Chen, L.; Cai, L.; Zhang, X.; Rich, A.

1994-01-01

The crystal structure of d(C4) solved at 2.3-A resolution reveals a four-stranded molecule composed of two interdigitated or intercalated duplexes. The duplexes are held together by hemiprotonated cytosine-cytosine base pairs and are parallel stranded, but the two duplexes point in opposite directions. The molecule has a slow right-handed twist of 12.4 degrees between covalently linked cytosine base pairs, and the base stacking distance is 3.1 A. This is in general agreement with the NMR studies. A biological role for DNA in this conformation is suggested.

X-ray-structure of a cytidylyl-3',5'-adenosine-proflavine complex: a self-paired parallel-chain double helical dimer with an intercalated acridine dye.

PubMed Central

Westhof, E; Sundaralingam, M

1980-01-01

The non-self-complementary dinucleoside monophosphate cytidylyl-3',5'-adenosine (CpA) forms a base-paired parallel-chain dimer with an intercalated proflavine. The dimer complex possesses a right-handed helical twist. The dimer helix has an irregular girth with a neutral adenine-adenine (A-A) pair, hydrogen-bonded through the N6 and N7 sites (C1'...C1' separation of 10.97 A), and a triply hydrogen-bonded protonated cytosine-cytosine (C-C) pair with a proton shared between the base N3 sites (Cl'...Cl' separation of 9.59 A). The torsion angles of the sugar-phosphate backbone are within their most preferred ranges and the sugar puckering sequence (5' leads to 3') is C3'-endo, C2'-endo. There is also a second proflavine molecule sandwiched between CpA dimers on the 21-axis. Both proflavines are necessarily disordered, being on dyad axis, and this suggests possible insights into the dynamics of intercalation of planar drugs. This structure shows that intercalation of planar drugs in nucleic acids may not be restricted to antiparallel complementary Watson-Crick pairing regions and provides additional mechanisms for acridine mutagenesis. PMID:6929524

Thermally Induced Lateral Motion of α-Zirconium Phosphate Layers Intercalated with Hexadecylamines

NASA Astrophysics Data System (ADS)

Char, Kookheon

2005-03-01

Well-defined intercalated structure, either interdigitated layers or bilayers, of hexadecylamines (HDAs) in a confined space of a highly-functionalized layered material, α- zirconium phosphate (α-ZrP), was prepared and these two distinct intercalated structures can serve as model systems to investigate the interaction of the two monolayers whose amphiphilic tails are adjacent to each other. Acidic functional groups (-POH) on the α-ZrP are in well-ordered array and the number of functional group is quite high (i.e., cationic exchange capacity (CEC) = 664 mmole/100 g, area per one charge site = 0.24 nm^2) enough to realize the bilayers (i.e., discrete two monolayers) of HDAs within the α-ZrP interlayer. We employed the two-step intercalation mechanism for the preparation of well- ordered interdigitated layers as well as the bilayers of alkyl chains attached to both sides of the α-ZrP intergallery. An intriguing lateral motion of the α-ZrP sheets was observed with in-situ SAXS measurements for the interdigitated layer during heating and cooling cycle and verified with TEM. This lateral motion is believed to be due to the transition from the tilted to the untilted conformation of the interdigitated HDA chains and this transition is found to be thermally reversible.

Correlation of intercalation potential with d-electron configurations for cathode compounds of lithium-ion batteries.

PubMed

Chen, Zhenlian; Zhang, Caixia; Zhang, Zhiyong; Li, Jun

2014-07-14

The d-electron localization is widely recognized as important to transport properties of transition metal compounds, but its role in the energy conversion of intercalation reactions of cathode compounds is still not fully explored. In this work, the correlation of intercalation potential with electron affinity, a key energy term controlling electron intercalation, then with d-electron configuration, is investigated. Firstly, we find that the change of the intercalation potential with respect to the transition metal cations within the same structure class is correlated in an approximately mirror relationship with the electron affinity, based on first-principles calculations on three typical categories of cathode compounds including layered oxides and polyoxyanions Then, by using a new model Hamiltonian based on the crystal-field theory, we reveal that the evolution is governed by the combination of the crystal-field splitting and the on-site d-d exchange interactions. Further, we show that the charge order in solid-solution composites and the compatibility of multi-electron redox steps could be inferred from the energy terms with the d-electron configuration alternations. These findings may be applied to rationally designing new chemistry for the lithium-ion batteries and other metal-ion batteries.

Capacitive Sensing of Intercalated H2O Molecules Using Graphene.

PubMed

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.

Intercalation compounds and electrodes for batteries

DOEpatents

Chiang, Yet-Ming; Sadoway, Donald R.; Jang, Young-Il; Huang, Biyan

2004-09-07

This invention concerns intercalation compounds and in particular lithium intercalation compounds which have improved properties for use in batteries. Compositions of the invention include particulate metal oxide material having particles of multicomponent metal oxide, each including an oxide core of at least first and second metals in a first ratio, and each including a surface coating of metal oxide or hydroxide that does not include the first and second metals in the first ratio formed by segregation of at least one of the first and second metals from the core. The core may preferably comprise Li.sub.x M.sub.y N.sub.z O.sub.2 wherein M and N are metal atom or main group elements, x, y and z are numbers from about 0 to about 1 and y and z are such that a formal charge on M.sub.y N.sub.z portion of the compound is (4-x), and having a charging voltage of at least about 2.5V. The invention may also be characterized as a multicomponent oxide microstructure usable as a lithium intercalation material including a multiphase oxide core and a surface layer of one material, which is a component of the multiphase oxide core, that protects the underlying intercalation material from chemical dissolution or reaction. In a particular preferred example the multicomponent oxide may be an aluminum-doped lithium manganese oxide composition. Such aluminum-doped lithium manganese oxide compositions, having an orthorhombic structure, also form a part of the invention. In addition, the invention includes articles, particularly electrodes, for batteries formed from the compositions of the invention, and batteries including such electrodes. The invention further relates to a composite intercalation material comprising at least two compounds in which at least one compound has an orthorhombic structure Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2, where y is nonzero, or a mixture of orthorhombic and monoclinic Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2.

Transition Metal Intercalators as Anticancer Agents—Recent Advances

PubMed Central

Deo, Krishant M.; Pages, Benjamin J.; Ang, Dale L.; Gordon, Christopher P.; Aldrich-Wright, Janice R.

2016-01-01

The diverse anticancer utility of cisplatin has stimulated significant interest in the development of additional platinum-based therapies, resulting in several analogues receiving clinical approval worldwide. However, due to structural and mechanistic similarities, the effectiveness of platinum-based therapies is countered by severe side-effects, narrow spectrum of activity and the development of resistance. Nonetheless, metal complexes offer unique characteristics and exceptional versatility, with the ability to alter their pharmacology through facile modifications of geometry and coordination number. This has prompted the search for metal-based complexes with distinctly different structural motifs and non-covalent modes of binding with a primary aim of circumventing current clinical limitations. This review discusses recent advances in platinum and other transition metal-based complexes with mechanisms of action involving intercalation. This mode of DNA binding is distinct from cisplatin and its derivatives. The metals focused on in this review include Pt, Ru and Cu along with examples of Au, Ni, Zn and Fe complexes; these complexes are capable of DNA intercalation and are highly biologically active. PMID:27809241

Electrochemical and Spectroscopic Analysis of Mg2+ Intercalation into Thin Film Electrodes of Layered Oxides: V2O5 and MoO3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gershinsky, G; Yoo, HD; Gofer, Y

Electrochemical, surface, and structural studies related to rechargeable Mg batteries were carried out with monolithic thin-film cathodes comprising layered V2O5 and MoO3. The reversible intercalation reactions of these electrodes with Mg ion in nonaqueous Mg salt solutions were explored using a variety of analytical tools. These included slow-scan rate cyclic voltammetry (SSCV), chrono-potentiometry (galvanostatic cycling), Raman and photoelectron spectroscopies, high-resolution microscopy, and XRD. The V2O5 electrodes exhibited reversible Mg-ion intercalation at capacities around 150-180 mAh g(-1) with 100% efficiency. A capacity of 220 mAh g(-1) at >95% efficiency was obtained with MoO3 electrodes. By applying the electrochemical driving force sufficientlymore » slowly it was possible to measure the electrodes at equilibrium conditions and verify by spectroscopy, microscopy, and diffractometry that these electrodes undergo fully reversible structural changes upon Mg-ion insertion/deinsertion cycling.« less

Mechanism Responsible for Intercalation of Dimethyl Sulfoxide in Kaolinite: Molecular Dynamics Simulations.

PubMed

Zhang, Shuai; Liu, Qinfu; Cheng, Hongfei; Gao, Feng; Liu, Cun; Teppen, Brian J

2018-01-01

Intercalation is the promising strategy to expand the interlayer region of kaolinite for their further applications. Herein, the adaptive biasing force (ABF) accelerated molecular dynamics simulations were performed to calculate the free energies involved in the kaolinite intercalation by dimethyl sulfoxide (DMSO). Additionally, the classical all atom molecular dynamics simulations were carried out to calculate the interfacial interactions between kaolinite interlayer surfaces and DMSO with the aim at exploring the underlying force that drives the DMSO to enter the interlayer space. The results showed that the favorable interaction of DMSO with both kaolinite interlayer octahedral surface and tetrahedral surface can help in introducing DMSO enter kaolinite interlayer. The hydroxyl groups on octahedral surface functioned as H-donors attracting the S=O groups of DMSO through hydrogen bonding interaction. The tetrahedral surface featuring hydrophobic property attracted the methyl groups of DMSO through hydrophobic interaction. The results provided a detailed picture of the energetics and interlayer structure of kaolinite-DMSO intercalate.

Incommensurate Graphene Foam as a High Capacity Lithium Intercalation Anode

PubMed Central

Paronyan, Tereza M.; Thapa, Arjun Kumar; Sherehiy, Andriy; Jasinski, Jacek B.; Jangam, John Samuel Dilip

2017-01-01

Graphite’s capacity of intercalating lithium in rechargeable batteries is limited (theoretically, 372 mAh g−1) due to low diffusion within commensurately-stacked graphene layers. Graphene foam with highly enriched incommensurately-stacked layers was grown and applied as an active electrode in rechargeable batteries. A 93% incommensurate graphene foam demonstrated a reversible specific capacity of 1,540 mAh g−1 with a 75% coulombic efficiency, and an 86% incommensurate sample achieves above 99% coulombic efficiency exhibiting 930 mAh g−1 specific capacity. The structural and binding analysis of graphene show that lithium atoms highly intercalate within weakly interacting incommensurately-stacked graphene network, followed by a further flexible rearrangement of layers for a long-term stable cycling. We consider lithium intercalation model for multilayer graphene where capacity varies with N number of layers resulting LiN+1C2N stoichiometry. The effective capacity of commonly used carbon-based rechargeable batteries can be significantly improved using incommensurate graphene as an anode material. PMID:28059110

Pulsed laser deposition of functionalized Mg-Al layered double hydroxide thin films

NASA Astrophysics Data System (ADS)

Vlad, A.; Birjega, R.; Tirca, I.; Matei, A.; Mardare, C. C.; Hassel, A. W.; Nedelcea, A.; Dinescu, M.; Zavoianu, R.

2018-02-01

In this paper, magnesium-aluminium layered double hydroxide (LDH) has been functionalized with sodium dodecyl sulfate (DS) and deposited as thin film by pulsed laser deposition (PLD). Mg, Al-LDH powders were prepared by co-precipitation and used as reference material. Intercalation of DS as an anionic surfactant into the LDHs host layers has been prepared in two ways: co-precipitation (P) and reconstruction (R). DS intercalation occurred in LDH powder via both preparation methods. The films deposited via PLD, in particular at 532 and 1064 nm, preserve the organic intercalated layered structure of the targets prepared from these powders. The results reveal the ability of proposed deposition technique to produce functional composite organo-modified LDHs thin films.

Defect-mediated, thermally-activated encapsulation of metals at the surface of graphite

DOE PAGES

Zhou, Yinghui; Lii-Rosales, Ann; Kim, Minsung; ...

2017-11-04

Here, we show that 3 metals – Dy, Ru, and Cu – can form multilayer intercalated (encapsulated) islands at the graphite (0001) surface if 2 specific conditions are met: Defects are introduced on the graphite terraces to act as entry portals, and the metal deposition temperature is well above ambient. Focusing on Dy as a prototype, we show that surface encapsulation is much different than bulk intercalation, because the encapsulated metal takes the form of bulk-like rafts of multilayer Dy, rather than the dilute, single-layer structure known for the bulk compound. Carbon-covered metallic rafts even form for relatively unreactive metalsmore » (Ru and Cu) which have no known bulk intercalation compound.« less

Ultrastructural and biochemical localization of N-RAP at the interface between myofibrils and intercalated disks in the mouse heart.

PubMed

Zhang, J Q; Elzey, B; Williams, G; Lu, S; Law, D J; Horowits, R

2001-12-11

N-RAP is a recently discovered muscle-specific protein found at cardiac intercalated disks. Double immunogold labeling of mouse cardiac muscle reveals that vinculin is located immediately adjacent to the fascia adherens region of the intercalated disk membrane, while N-RAP extends approximately 100 nm further toward the interior of the cell. We partially purified cardiac intercalated disks using low- and high-salt extractions followed by density gradient centrifugation. Immunoblots show that this preparation is highly enriched in desmin and junctional proteins, including N-RAP, talin, vinculin, beta1-integrin, N-cadherin, and connexin 43. Electron microscopy and immunolabeling demonstrate that N-RAP and vinculin are associated with the large fragments of intercalated disks that are present in this preparation, which also contains numerous membrane vesicles. Detergent treatment of the partially purified intercalated disks removed the membrane vesicles and extracted vinculin and beta1-integrin. Further separation on a sucrose gradient removed residual actin and myosin and yielded a fraction morphologically similar to fasciae adherentes that was highly enriched in N-RAP, N-cadherin, connexin 43, talin, desmin, and alpha-actinin. The finding that N-RAP copurifies with detergent-extracted intercalated disk fragments even though beta-integrin and vinculin have been completely removed suggests that N-RAP association with the adherens junction region is mediated by the cadherin system. Consistent with this hypothesis, we found that recombinant N-RAP fragments bind alpha-actinin in a gel overlay assay. In addition, immunofluorescence shows that N-RAP remains bound at the ends of isolated, detergent-treated cardiac myofibrils. These results demonstrate that N-RAP remains tightly bound to myofibrils and fasciae adherentes during biochemical purification and may be a key constituent in the mechanical link between these two structures.

Efficient phosphate sequestration for water purification by unique sandwich-like MXene/magnetic iron oxide nanocomposites

NASA Astrophysics Data System (ADS)

Zhang, Qingrui; Teng, Jie; Zou, Guodong; Peng, Qiuming; Du, Qing; Jiao, Tifeng; Xiang, Jianyong

2016-03-01

Rationally tailored intercalation for two-dimensional (2D) layered MXene materials has aroused extraordinary enthusiasm for broadening their applications. Herein, a novel sandwiched structural 2D MXene-iron oxide (MXI) material, prepared by selectively exfoliating an Al layer followed by magnetic ferric oxide intercalation, exhibits remarkable applicability to trace phosphate sequestration in the environmental remediation realm. Compared with commercial adsorbents, the resultant MXI nanocomposite exhibits a fast separation in 120 s together with the superior treatment capacities of 2100 kg and 2400 kg per kg in simulated and real phosphate wastewater applications, respectively. Such efficient sequestration is ascribed to the formation of a unique nano-ferric oxide morphology. The ultrafine nano-Fe2O3 particles can intercalate into the interior layers of MXene, widening the layer distance, and stimulating the available overlapping activated layers; while the efficient phosphate removal can be achieved by the strong complexation onto the embedded magnetic nano-Fe3O4 with a unique sandwich-structure as well as the stimulated Ti-O terminal within MXene. Apart from the fact that this approach suggests a complementary means for environmental remediation, it opens a new trajectory to achieve the functionalization of MXene.Rationally tailored intercalation for two-dimensional (2D) layered MXene materials has aroused extraordinary enthusiasm for broadening their applications. Herein, a novel sandwiched structural 2D MXene-iron oxide (MXI) material, prepared by selectively exfoliating an Al layer followed by magnetic ferric oxide intercalation, exhibits remarkable applicability to trace phosphate sequestration in the environmental remediation realm. Compared with commercial adsorbents, the resultant MXI nanocomposite exhibits a fast separation in 120 s together with the superior treatment capacities of 2100 kg and 2400 kg per kg in simulated and real phosphate wastewater applications, respectively. Such efficient sequestration is ascribed to the formation of a unique nano-ferric oxide morphology. The ultrafine nano-Fe2O3 particles can intercalate into the interior layers of MXene, widening the layer distance, and stimulating the available overlapping activated layers; while the efficient phosphate removal can be achieved by the strong complexation onto the embedded magnetic nano-Fe3O4 with a unique sandwich-structure as well as the stimulated Ti-O terminal within MXene. Apart from the fact that this approach suggests a complementary means for environmental remediation, it opens a new trajectory to achieve the functionalization of MXene. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr09303a

Electronic structure ‘engineering’ in the development of materials for Li-ion and Na-ion batteries

NASA Astrophysics Data System (ADS)

Molenda, Janina

2017-03-01

Transition metal oxides with a general formula A x M a O b (A  =  Li, Na, M  =  transition metal) constitute a group of potential electrode materials for a new generation of alkaline batteries. This application is related to the fact that these compounds can reversibly intercalate high amounts of alkaline ions (1 or more moles per mole of M a O b ) already at room temperature, without significant changes in their crystallographic structure. The author of this work basing on her own investigations of A x M a O b (A  =  Li, Na; M  =  3d, 4d, 5d) has demonstrated that the electronic structure of these materials plays an important role in the intercalation process. Electronic model of intercalation process is presented. Author’s studies show that electronic structure ‘engineering’ is an excellent method of controlling properties of the cathode materials for Li-ion and Na-ion batteries, changing their unfavorable character of the discharge curve, from step-like to monotonic, through modification and control density of states function of a cathode material. Keynote talk at 8th International Workshop on Advanced Materials Science and Nanotechnology (IWAMSN2016), 8-12 November 2016, Ha Long City, Vietnam.

A ruthenium dimer complex with a flexible linker slowly threads between DNA bases in two distinct steps.

PubMed

Bahira, Meriem; McCauley, Micah J; Almaqwashi, Ali A; Lincoln, Per; Westerlund, Fredrik; Rouzina, Ioulia; Williams, Mark C

2015-10-15

Several multi-component DNA intercalating small molecules have been designed around ruthenium-based intercalating monomers to optimize DNA binding properties for therapeutic use. Here we probe the DNA binding ligand [μ-C4(cpdppz)2(phen)4Ru2](4+), which consists of two Ru(phen)2dppz(2+) moieties joined by a flexible linker. To quantify ligand binding, double-stranded DNA is stretched with optical tweezers and exposed to ligand under constant applied force. In contrast to other bis-intercalators, we find that ligand association is described by a two-step process, which consists of fast bimolecular intercalation of the first dppz moiety followed by ∼10-fold slower intercalation of the second dppz moiety. The second step is rate-limited by the requirement for a DNA-ligand conformational change that allows the flexible linker to pass through the DNA duplex. Based on our measured force-dependent binding rates and ligand-induced DNA elongation measurements, we are able to map out the energy landscape and structural dynamics for both ligand binding steps. In addition, we find that at zero force the overall binding process involves fast association (∼10 s), slow dissociation (∼300 s), and very high affinity (Kd ∼10 nM). The methodology developed in this work will be useful for studying the mechanism of DNA binding by other multi-step intercalating ligands and proteins. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Direct intercalation of cisplatin into zirconium phosphate nanoplatelets for potential cancer nanotherapy

PubMed Central

Díaz, Agustín; González, Millie L.; Pérez, Riviam J.; David, Amanda; Mukherjee, Atashi; Báez, Adriana; Clearfield, Abraham

2014-01-01

We report the use of zirconium phosphate nanoplatelets (ZrP) for the encapsulation of the anticancer drug cisplatin and its delivery to tumor cells. Cisplatin was intercalated into ZrP by direct-ion exchange and was tested in-vitro for cytotoxicity in the human breast cancer (MCF-7) cell line. The structural characterization of the intercalated cisplatin in ZrP suggests that during the intercalation process, the chloride ligands of the cisplatin complex were substituted by phosphate groups within the layers. Consequently, a new phosphate phase with the platinum complex directly bound to ZrP (cisPt@ZrP) is produced with an interlayer distance of 9.3 Å. The in-vitro release profile of the intercalated drug by pH stimulus shows that at low pH under lysosomal conditions the platinum complex is released with simultaneous hydrolysis of the zirconium phosphate material, while at higher pH the complex is not released. Experiments with the MCF-7 cell line show that cisPt@ZrP reduced the cell viability up to 40%. The cisPt@ZrP intercalation product is envisioned as a future nanotherapy agent for cancer. Taking advantage of the shape and sizes of the ZrP particles and controlled release of the drug at low pH, it is intended to exploit the enhanced permeability and retention effect of tumors, as well as their intrinsic acidity, for the destruction of malignant cells. PMID:24072038

Regulation of proximal-distal intercalation during limb regeneration in the axolotl (Ambystoma mexicanum).

PubMed

Satoh, Akira; Cummings, Gillian M C; Bryant, Susan V; Gardiner, David M

2010-12-01

Intercalation is the process whereby cells located at the boundary of a wound interact to stimulate proliferation and the restoration of the structures between the boundaries that were lost during wounding. Thus, intercalation is widely considered to be the mechanism of regeneration. When a salamander limb is amputated, the entire cascade of regeneration events is activated, and the missing limb segments and their boundaries (joints) as well as the structures within each segment are regenerated. Therefore, in an amputated limb it is not possible to distinguish between intersegmental regeneration (formation of new segments/joints) and intrasegmental regeneration (formation of structures within a given segment), and it is not possible to study the differential regulation of these two processes. We have used two models for regeneration that allow us to study these two processes independently, and report that inter- and intrasegmental regeneration are different processes regulated by different signaling pathways. New limb segments/joints can be regenerated from cells that dedifferentiate to form blastema cells in response to signaling that is mediated in part by fibroblast growth factor. © 2010 The Authors. Journal compilation © 2010 Japanese Society of Developmental Biologists.

Graphene/MoS2 heterostructures as templates for growing two-dimensional metals: Predictions from ab initio calculations

NASA Astrophysics Data System (ADS)

Šljivančanin, Željko; Belić, Milivoj

2017-09-01

Preparation of single-atom-thick layers of ordinary metals has been a challenging task since their closely packed atoms lack layered structure with highly anisotropic bonding. Using computational modeling based on density functional theory we showed that graphene/MoS2 heterostructures can be used as suitable templates to grow stable two-dimensional (2D) clusters, as well as extended monoatomic layers of metals with nonlayered structure in the bulk. Considering gold and lithium as two metals with markedly different properties, we found that Li intercalants strengthen coupling between graphene (G) and MoS2, mainly due to electrostatic attraction of 2D materials with positively charged Li atoms. However, intercalation with large Au atoms gives rise to a significant increase in the distance between G and MoS2 and thus, weakens their interaction. In addition to strong preference for 2D growth, we demonstrated that Au intercalants weakly interact with both G and MoS2, and hence G /MoS2 vertical heterostructures could be a promising framework to prepare gold 2D structures with electronic properties closely resembling those of the hypothetical free-standing hexagonal gold monolayer.

Quasi-one-dimensional nanostructured cobalt (Co) intercalated vanadium oxide (V{sub 2}O{sub 5}): Peroxovanadate sol gel synthesis and structural study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langie da Silva, Douglas, E-mail: douglas.langie@ufpel.edu.br; Moreira, Eduardo Ceretta; Dias, Fábio Teixeira

2015-01-15

Nanostructured cobalt vanadium oxide (V{sub 2}O{sub 5}) xerogels spread onto crystalline Si substrates were synthesized via peroxovanadate sol gel route. The resulting products were characterized by distinct experimental techniques. The surface morphology and the nanostructure of xerogels correlate with Co concentration. The decrease of the structural coherence length is followed by the formation of a loose network of nanopores when the concentration of intercalated species was greater than 4 at% of Co. The efficiency of the synthesis route also drops with the increase of Co concentration. The interaction between the Co(OH{sub 2}){sub 6}{sup 2+} cations and the (H{sub 2}V{sub 10}O{submore » 28}){sup 4−} anions during the synthesis was suggested as a possible explanation for the incomplete condensation of the V{sub 2}O{sub 5} gel. Finally the experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5}. In this scenario two possible preferential occupation sites for the metallic atoms in the framework of the xerogel were proposed. - Graphical abstract: Quasi-one-dimensional nanostructured cobalt (Co) intercalated vanadium oxide (V{sub 2}O{sub 5}) nanoribbons synthesized by peroxovanadate sol gel route. - Highlights: • Nanostructured cobalt V{sub 2}O{sub 5} gel spread onto c{sub S}i were synthesized via peroxovanadate sol gel route. • The micro and nanostructure correlates with the cobalt content. • The efficiency of the synthesis route shows to be also dependent of Co content. • The experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5} xerogel.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang Hui; Zou Kang; Guo Shaohuan

A nanostructural drug-inorganic clay composite involving a pharmaceutically active compound captopril (Cpl) intercalated Mg-Al-layered double hydroxides (Cpl-LDHs) with Mg/Al molar ratio of 2.06 has been assembled by coprecipitation method. Powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR) and Raman spectra analysis indicate a successful intercalation of Cpl between the layers with a vertical orientation of Cpl disulphide-containing S-S linkage. SEM photo indicates that as-synthesized Cpl-LDHs possess compact and non-porous structure with approximately and linked elliptical shape particles of ca. 50 nm. TG-DTA analyses suggest that the thermal stability of intercalated organic species is largely enhanced due to host-guest interactionmore » involving the hydrogen bond compared to pure form before intercalation. The in vitro release studies show that both the release rate and release percentages markedly decrease with increasing pH from 4.60 to 7.45 due to possible change of release mechanism during the release process. The kinetic simulation for the release data, and XRD and FT-IR analyses for samples recovered from release media indicate that the dissolution mechanism is mainly responsible for the release behaviour of Cpl-LDHs at pH 4.60, while the ion-exchange one is responsible for that at pH 7.45. - Graphical abstract: Based on XRD, FT-IR and Raman spectra analyses, it is suggested that captopril (Cpl) exists as its disulphide metabolites in the interlayer of Mg-Al-LDHs via hydrogen bonding between guest carboxylate function and hydroxyl group of the host layers. A schematic supramolecular structure of Cpl intercalates involving a vertical orientation of Cpl disulphide-containing S-S bond between the layers with carboxylate anions pointing to both hydroxide layers is presented.« less

Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

NASA Technical Reports Server (NTRS)

Hung, Ching-Chen; Prisko, Aniko

1999-01-01

The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

Intermolecular interactions between imidazole derivatives intercalated in layered solids. Substituent group effect

DOE Office of Scientific and Technical Information (OSTI.GOV)

González, M.; Lemus-Santana, A.A.; Rodríguez-Hernández, J.

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. Thesemore » 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.« less

First-principles theory of cation- and intercalation-ordering in Li_xCoO_2

NASA Astrophysics Data System (ADS)

Wolverton, C.; Zunger, Alex

1998-03-01

Using a combination of first-principles total energies, a cluster expansion technique, and Monte Carlo simulations, we present a first-principles theory which can predict both cation- and intercalation-ordering patterns at both zero and finite temperatures, and can provide first-principles predictions of battery voltages of Li_xCoO_2/Li cells. The classes of ordering problems that we study are the following: (i) The LiMO2 oxides (M=3d metal) form a series of structures based on an octahedrally-coordinated network with anions (O) on one fcc sublattice and cations (Li and M) on the other, leading to Li/Co ordering in LiCoO2 (x=1). We find the ground state is the CuPt or (111)-layered cation arrangment, in agreement with the observed structure. (ii) In battery applications, Li is (de)intercalated from the compound, creating a vacancy (denoted Box) that can be positioned in different lattice locations; Thus, Box/Co ordering in BoxCoO2 (x=0) is also of interest. We find the ground state for BoxCoO2 is also a (111)-layered structure, although a different stacking sequence (AAA) of close-packed layers is preferred. (iii) The vacancies left behind by Li extraction can form ordered vacancy compounds in partially de-lithiated Li_xCoO_2, leading to a Box/Li ordering problem (0<=x<=1). Our calculations agree with the observed voltage profiles in these systems, and predict the existence of new intercalation-ordered compounds. Supported by BES/OER/DMS under contract DE-AC36-83CH10093.

Combination probes with intercalating anchors and proximal fluorophores for DNA and RNA detection

PubMed Central

Qiu, Jieqiong; Wilson, Adam; El-Sagheer, Afaf H.; Brown, Tom

2016-01-01

A new class of modified oligonucleotides (combination probes) has been designed and synthesised for use in genetic analysis and RNA detection. Their chemical structure combines an intercalating anchor with a reporter fluorophore on the same thymine nucleobase. The intercalator (thiazole orange or benzothiazole orange) provides an anchor, which upon hybridisation of the probe to its target becomes fluorescent and simultaneously stabilizes the duplex. The anchor is able to communicate via FRET to a proximal reporter dye (e.g. ROX, HEX, ATTO647N, FAM) whose fluorescence signal can be monitored on a range of analytical devices. Direct excitation of the reporter dye provides an alternative signalling mechanism. In both signalling modes, fluorescence in the unhybridised probe is switched off by collisional quenching between adjacent intercalator and reporter dyes. Single nucleotide polymorphisms in DNA and RNA targets are identified by differences in the duplex melting temperature, and the use of short hybridization probes, made possible by the stabilisation provided by the intercalator, enhances mismatch discrimination. Unlike other fluorogenic probe systems, placing the fluorophore and quencher on the same nucleobase facilitates the design of short probes containing multiple modifications. The ability to detect both DNA and RNA sequences suggests applications in cellular imaging and diagnostics. PMID:27369379

Local corrugation and persistent charge density wave in ZrTe 3 with Ni intercalation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganose, Alex M.; Gannon, Liam; Fabrizi, Federica

Here, the mechanism of emergent bulk superconductivity in transition-metal intercalated ZrTe 3 is investigated by studying the effect of Ni doping on the band structure and charge density wave (CDW). The study reports theoretical and experimental results in the range of Ni 0.01ZrTe 3 to Ni 0.05ZrTe 3. In the highest doped samples, bulk superconductivity with T c < T CDW is observed, with a reduced T CDW compared with pure ZrTe 3. Relativistic ab initio calculations reveal that Ni incorporation occurs preferentially through intercalation in the van der Waals gap. Analysis of the structural and electronic effects of intercalationmore » indicate buckling of the Te sheets adjacent to the Ni site akin to a locally stabilized CDW-like lattice distortion. In contrast to the changes of T CDW observed in resistivity, experiments with low-temperature x-ray diffraction, angle-resolved-photoemission spectroscopy, as well as temperature-dependent resistivity reveal the nearly unchanged persistence of the CDW into the regime of bulk superconductivity. The CDW gap is found to be unchanged in its extent in momentum space, with the gap size also unchanged or possibly slightly reduced upon Ni intercalation. Both experimental observations suggest that superconductivity coexists with the CDW in Ni xZrTe 3.« less

Local corrugation and persistent charge density wave in ZrTe 3 with Ni intercalation

DOE PAGES

Ganose, Alex M.; Gannon, Liam; Fabrizi, Federica; ...

2018-04-03

Here, the mechanism of emergent bulk superconductivity in transition-metal intercalated ZrTe 3 is investigated by studying the effect of Ni doping on the band structure and charge density wave (CDW). The study reports theoretical and experimental results in the range of Ni 0.01ZrTe 3 to Ni 0.05ZrTe 3. In the highest doped samples, bulk superconductivity with T c < T CDW is observed, with a reduced T CDW compared with pure ZrTe 3. Relativistic ab initio calculations reveal that Ni incorporation occurs preferentially through intercalation in the van der Waals gap. Analysis of the structural and electronic effects of intercalationmore » indicate buckling of the Te sheets adjacent to the Ni site akin to a locally stabilized CDW-like lattice distortion. In contrast to the changes of T CDW observed in resistivity, experiments with low-temperature x-ray diffraction, angle-resolved-photoemission spectroscopy, as well as temperature-dependent resistivity reveal the nearly unchanged persistence of the CDW into the regime of bulk superconductivity. The CDW gap is found to be unchanged in its extent in momentum space, with the gap size also unchanged or possibly slightly reduced upon Ni intercalation. Both experimental observations suggest that superconductivity coexists with the CDW in Ni xZrTe 3.« less

The Pekin duck programmed death-ligand 1: cDNA cloning, genomic structure, molecular characterization and mRNA expression analysis.

PubMed

Yao, Q; Fischer, K P; Tyrrell, D L; Gutfreund, K S

2015-04-01

Programmed death ligand-1 (PD-L1) plays an important role in the attenuation of adaptive immune responses in higher vertebrates. Here, we describe the identification of the Pekin duck PD-L1 orthologue (duPD-L1) and its gene structure. The duPD-L1 cDNA encodes a 311-amino acid protein that has an amino acid identity of 78% and 42% with chicken and human PD-L1, respectively. Mapping of the duPD-L1 cDNA with duck genomic sequences revealed an exonic structure of its coding sequence similar to those of other vertebrates but lacked a noncoding exon 1. Homology modelling of the duPD-L1 extracellular domain was compatible with the tandem IgV-like and IgC-like IgSF domain structure of human PD-L1 (PDB ID: 3BIS). Residues known to be important for receptor binding of human PD-L1 were mostly conserved in duPD-L1 within the N-terminus and the G sheet, and partially conserved within the F sheet but not within sheets C and C'. DuPD-L1 mRNA was constitutively expressed in all tissues examined with highest expression levels in lung and spleen and very low levels of expression in muscle, kidney and brain. Mitogen stimulation of duck peripheral blood mononuclear cells transiently increased duPD-L1 mRNA expression. Our observations demonstrate evolutionary conservation of the exonic structure of its coding sequence, the extracellular domain structure and residues implicated in receptor binding, but the role of the longer cytoplasmic tail in avian PD-L1 proteins remains to be determined. © 2014 John Wiley & Sons Ltd.

The capacity fading mechanism and improvement of cycling stability in MoS2-based anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Shu, Haibo; Li, Feng; Hu, Chenli; Liang, Pei; Cao, Dan; Chen, Xiaoshuang

2016-01-01

Two-dimensional (2D) layered MoS2 nanosheets possess great potential as anode materials for lithium ion batteries (LIBs), but they still suffer from poor cycling performance. Improving the cycling stability of electrode materials depends on a deep understanding of their dynamic structural evolution and reaction kinetics in the lithiation process. Herein, thermodynamic phase diagrams and the lithiation dynamics of MoS2-based nanostructures with the intercalation of lithium ions are studied by using first-principles calculations and ab initio molecular dynamics simulations. Our results demonstrate that the continuous intercalation of Li ions induces structural destruction of 2H phase MoS2 nanosheets in the discharge process that follows a layer-by-layer dissociation mechanism. Meanwhile, the intercalation of Li ions leads to a structural transition of MoS2 nanosheets from the 2H to the 1T phase due to the ultralow transition barriers (~0.1 eV). We find that the phase transition can slow down the dissociation of MoS2 nanosheets during lithiation. The result can be applied to explain extensive experimental observation of the fast capacity fading of MoS2-based anode materials between the first and the subsequent discharges. To suppress the dissociation of MoS2 nanosheets in the lithiation process, we propose a strategy by constructing a sandwich-like graphene/MoS2/graphene structure that indicates high chemical stability, superior conductivity, and high Li-ion mobility in the charge/discharge process, implying the possibility to induce an improvement in the anode cycling performance. This work opens a new route to rational design layered transition-metal disulfide (TMD) anode materials for LIBs with superior cycling stability and electrochemical performance.Two-dimensional (2D) layered MoS2 nanosheets possess great potential as anode materials for lithium ion batteries (LIBs), but they still suffer from poor cycling performance. Improving the cycling stability of electrode materials depends on a deep understanding of their dynamic structural evolution and reaction kinetics in the lithiation process. Herein, thermodynamic phase diagrams and the lithiation dynamics of MoS2-based nanostructures with the intercalation of lithium ions are studied by using first-principles calculations and ab initio molecular dynamics simulations. Our results demonstrate that the continuous intercalation of Li ions induces structural destruction of 2H phase MoS2 nanosheets in the discharge process that follows a layer-by-layer dissociation mechanism. Meanwhile, the intercalation of Li ions leads to a structural transition of MoS2 nanosheets from the 2H to the 1T phase due to the ultralow transition barriers (~0.1 eV). We find that the phase transition can slow down the dissociation of MoS2 nanosheets during lithiation. The result can be applied to explain extensive experimental observation of the fast capacity fading of MoS2-based anode materials between the first and the subsequent discharges. To suppress the dissociation of MoS2 nanosheets in the lithiation process, we propose a strategy by constructing a sandwich-like graphene/MoS2/graphene structure that indicates high chemical stability, superior conductivity, and high Li-ion mobility in the charge/discharge process, implying the possibility to induce an improvement in the anode cycling performance. This work opens a new route to rational design layered transition-metal disulfide (TMD) anode materials for LIBs with superior cycling stability and electrochemical performance. Electronic supplementary information (ESI) available: Models and energetics of Li adsorption/intercalation onto MoS2 sheets, details of the phase diagram calculations, schematic illustration for the structural evolution of lithiated MoS2 nanosheets, AIMD trajectories for lithiated silicene/MoS2/silicene composites, and movies for recording the AIMD simulation results. See DOI: 10.1039/c5nr07909h

Indirect measurement of N-14 quadrupolar coupling for NH3 intercalated in potassium graphite

NASA Technical Reports Server (NTRS)

Tsang, T.; Fronko, R. M.; Resing, H. A.

1987-01-01

A method for indirect measurement of the nuclear quadrupolar coupling was developed and applied to NH3 molecules in the graphite intercalation compound K(NH3)4.3C24, which has a layered structure with alternating carbon and intercalant layers. Three triplets were observed in the H-1 NMR spectra of the compound. The value of the N-14 quadrupolar coupling constant of NH3 (3.7 MHz), determined indirectly from the H-1 NMR spectra, was intermediate between the gas value of 4.1 MHz and the solid-state value of 3.2 MHz. The method was also used to deduce the (H-1)-(H-1) and (N-14)-(H-1) dipolar interactions, the H-1 chemical shifts, and the molecular orientations and motions of NH3.

Three-Dimensional Intercalated Porous Graphene on Si(111)

NASA Astrophysics Data System (ADS)

Pham, Trung T.; Sporken, Robert

2018-02-01

Three-dimensional intercalated porous graphene has been formed on Si(111) by electron beam evaporation under appropriate conditions and its structural and electronic properties investigated in detail by reflection high-energy electron diffraction, x-ray photoemission spectroscopy, Raman spectroscopy, high-resolution scanning electron microscopy, atomic force microscopy, and scanning tunneling microscopy. The results show that the crystalline quality of the porous graphene depended not only on the substrate temperature but also on the SiC layer thickness during carbon atom deposition.

A mediator-free glucose biosensor based on glucose oxidase/chitosan/α-zirconium phosphate ternary biocomposite.

PubMed

Liu, Li-Min; Wen, Jiwu; Liu, Lijun; He, Deyong; Kuang, Ren-yun; Shi, Taqing

2014-01-15

A novel glucose oxidase/chitosan/α-zirconium phosphate (GOD/chitosan/α-ZrP) ternary biocomposite was prepared by co-intercalating glucose oxidase (GOD) and chitosan into the interlayers of α-zirconium phosphate (α-ZrP) via a delamination-reassembly procedure. The results of X-ray diffraction, infrared spectroscopy, circular dichroism, and ultraviolet spectrum characterizations indicated not only the layered and hybrid structure of the GOD/chitosan/α-ZrP ternary biocomposite but also the recovered activity of the intercalated GOD improved by the co-intercalated chitosan. By depositing the GOD/chitosan/α-ZrP biocomposite film onto a glassy carbon electrode, the direct electrochemistry of the intercalated GOD was achieved with a fast electron transfer rate constant, k(s), of 7.48±3.52 s(-1). Moreover, this GOD/chitosan/α-ZrP biocomposite modified electrode exhibited a sensitive response to glucose in the linear range of 0.25-8.0 mM (R=0.9994, n=14), with a determination limit of 0.076 mM. Copyright © 2013 Elsevier Inc. All rights reserved.

AgI -Induced Switching of DNA Binding Modes via Formation of a Supramolecular Metallacycle.

PubMed

Basak, Shibaji; Léon, J Christian; Ferranco, Annaleizle; Sharma, Renu; Hebenbrock, Marian; Lough, Alan; Müller, Jens; Kraatz, Heinz-Bernhard

2018-03-12

The histidine derivative L1 of the DNA intercalator naphthalenediimide (NDI) forms a triangular Ag I complex (C2). The interactions of L1 and of C2 with DNA were studied by circular dichroism (CD) and UV/Vis spectroscopy and by viscosity studies. Different binding modes were observed for L1 and for C2, as the Ag I complex C2 is too large in size to act as an intercalator. If Ag I is added to the NDI molecule that is already intercalated into a duplex, higher order complexes are formed within the DNA duplex and cause disruptions in the helical duplex structure, which leads to a significant decrease in the characteristic CD features of B-DNA. Thus, via addition of a metal we show how a classic and well-known organic intercalator unit can be turned into a partial metallo insertor. We also show how electrochemical impedance spectroscopy (EIS) can be used to probe DNA binding modes on DNA films that are immobilized on gold surfaces. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of Zn-Ti layered double hydroxide intercalated with cinnamic acid for cosmetic application

NASA Astrophysics Data System (ADS)

Li, Yong; Tang, Liping; Ma, Xinxu; Wang, Xinrui; Zhou, Wei; Bai, Dongsheng

2017-08-01

The use of sunscreen is recently growing and their efficacy and safety must be taken into account since they are applied on the skin frequently. In this work, an organic ultraviolet (UV) ray absorbent, cinnamic acid (CA) was intercalated into Zn-Ti layered double hydroxide (LDH) by anion-exchange reaction. ZnTi-CA-LDH, a new type of host-guest UV-blocking material has been synthesized. Detailed structural and surface morphology of ZnTi-CA-LDH were characterized by XRD, FT-IR, SEM and TEM. ZnTi-CA-LDH exhibits a superior UV blocking ability compared to pure CA and ZnTi-CO3-LDH. The thermal stability of the intercalated ZnTi-CA-LDH was investigated by TG-DTA, which showed that the thermostability of CA was markedly enhanced after intercalation into ZnTi-CO3-LDH. The EPR data showed greatly decreased photocatalytic activity compared to common inorganic UV blocking agents TiO2 and ZnO. Furthermore, the sample was formulated in a sunscreen cream to study the matrix protective effect towards UV rays.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cursino, Ana Cristina Trindade, E-mail: anacursino@ufpr.br; Rives, Vicente, E-mail: vrives@usal.es; Arizaga, Gregorio Guadalupe Carbajal, E-mail: gregoriocarbajal@yahoo.com.mx

2015-10-15

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

First principles studies of structure stability and lithium intercalation of ZnCo2 O4

NASA Astrophysics Data System (ADS)

Zhang, Yanning; Liu, Weiwei; Beijing Computational Science Research Center Team

Among the metal oxides, which are the most widely investigated alternative anodes for use in lithium ion batteries (LIBs), binary and ternary transition metal oxides have received special attention due to their high capacity values. ZnCo2O4 is a promising candidate as anode for LIB, and one can expect a total capacity corresponding to 7.0 - 8.33 mol of recyclable Li per mole of ZnCo2O4. Here we studied the structural stability, electronic properties, lithium intercalation and diffusion barrier of ZnCo2O4 through density functional calculations. The calculated structural and energetic parameters are comparable with experiments. Our theoretical studies provide insights in understanding the mechanism of lithium ion displacement reactions in this ternary metal oxide.

Physicochemical characterization, and relaxometry studies of micro-graphite oxide, graphene nanoplatelets, and nanoribbons.

PubMed

Paratala, Bhavna S; Jacobson, Barry D; Kanakia, Shruti; Francis, Leonard Deepak; Sitharaman, Balaji

2012-01-01

The chemistry of high-performance magnetic resonance imaging contrast agents remains an active area of research. In this work, we demonstrate that the potassium permanganate-based oxidative chemical procedures used to synthesize graphite oxide or graphene nanoparticles leads to the confinement (intercalation) of trace amounts of Mn(2+) ions between the graphene sheets, and that these manganese intercalated graphitic and graphene structures show disparate structural, chemical and magnetic properties, and high relaxivity (up to 2 order) and distinctly different nuclear magnetic resonance dispersion profiles compared to paramagnetic chelate compounds. The results taken together with other published reports on confinement of paramagnetic metal ions within single-walled carbon nanotubes (a rolled up graphene sheet) show that confinement (encapsulation or intercalation) of paramagnetic metal ions within graphene sheets, and not the size, shape or architecture of the graphitic carbon particles is the key determinant for increasing relaxivity, and thus, identifies nano confinement of paramagnetic ions as novel general strategy to develop paramagnetic metal-ion graphitic-carbon complexes as high relaxivity MRI contrast agents.

Physicochemical Characterization, and Relaxometry Studies of Micro-Graphite Oxide, Graphene Nanoplatelets, and Nanoribbons

PubMed Central

Paratala, Bhavna S.; Jacobson, Barry D.; Kanakia, Shruti; Francis, Leonard Deepak; Sitharaman, Balaji

2012-01-01

The chemistry of high-performance magnetic resonance imaging contrast agents remains an active area of research. In this work, we demonstrate that the potassium permanganate-based oxidative chemical procedures used to synthesize graphite oxide or graphene nanoparticles leads to the confinement (intercalation) of trace amounts of Mn2+ ions between the graphene sheets, and that these manganese intercalated graphitic and graphene structures show disparate structural, chemical and magnetic properties, and high relaxivity (up to 2 order) and distinctly different nuclear magnetic resonance dispersion profiles compared to paramagnetic chelate compounds. The results taken together with other published reports on confinement of paramagnetic metal ions within single-walled carbon nanotubes (a rolled up graphene sheet) show that confinement (encapsulation or intercalation) of paramagnetic metal ions within graphene sheets, and not the size, shape or architecture of the graphitic carbon particles is the key determinant for increasing relaxivity, and thus, identifies nano confinement of paramagnetic ions as novel general strategy to develop paramagnetic metal-ion graphitic-carbon complexes as high relaxivity MRI contrast agents. PMID:22685555

Discrete Li-occupation versus pseudo-continuous Na-occupation and their relationship with structural change behaviors in Fe₂(MoO₄)₃

DOE PAGES

Yue, Ji-Li; Zhou, Yong-Ning; Shi, Si-Qi; ...

2015-03-06

The key factors governing the single-phase or multi-phase structural change behaviors during the intercalation/deintercalation of guest ions have not been well studied and understood yet. Through systematic studies of orthorhombic Fe₂(MoO₄)₃ electrode, two distinct guest ion occupation paths, namely discrete one for Li and pseudo-continuous one for Na, as well as their relationship with single-phase and two-phase modes for Na⁺ and Li⁺, respectively during the intercalation/deintercalation process have been demonstrated. For the first time, the direct atomic-scale observation of biphasic domains (discrete occupation) in partially lithiated Fe₂(MoO₄)₃ and the one by one Na occupation (pseudo-continuous occupation) at 8d sites inmore » partially sodiated Fe₂(MoO₄)₃ are obtained during the discharge processes of Li/Fe₂(MoO₄)₃ and Na/Fe₂(MoO₄)₃ cells respectively. Our combined experimental and theoretical studies bring the new insights for the research and development of intercalation compounds as electrode materials for secondary batteries.« less

Superconducting critical fields of alkali and alkaline-earth intercalates of MoS2

NASA Technical Reports Server (NTRS)

Woollam, J. A.; Somoano, R. B.

1976-01-01

Results are reported for measurements of the critical-field anisotropy and temperature dependence of group-VIB semiconductor MoS2 intercalated with the alkali and alkaline-earth metals Na, K, Rb, Cs, and Sr. The temperature dependences are compared with present theories on the relation between critical field and transition temperature in the clean and dirty limits over the reduced-temperature range from 1 to 0.1. The critical-field anisotropy data are compared with predictions based on coupled-layers and thin-film ('independent-layers') models. It is found that the critical-field boundaries are steep in all cases, that the fields are greater than theoretical predictions at low temperatures, and that an unusual positive curvature in the temperature dependence appears which may be related to the high anisotropy of the layer structure. The results show that materials with the largest ionic intercalate atom diameters and hexagonal structures (K, Rb, and Cs compounds) have the highest critical temperatures, critical fields, and critical-boundary slopes; the critical fields of these materials are observed to exceed the paramagnetic limiting fields.

Photoelectron Holographic Atomic Arrangement Imaging of Cleaved Bimetal-intercalated Graphite Superconductor Surface

PubMed Central

Matsui, Fumihiko; Eguchi, Ritsuko; Nishiyama, Saki; Izumi, Masanari; Uesugi, Eri; Goto, Hidenori; Matsushita, Tomohiro; Sugita, Kenji; Daimon, Hiroshi; Hamamoto, Yuji; Hamada, Ikutaro; Morikawa, Yoshitada; Kubozono, Yoshihiro

2016-01-01

From the C 1s and K 2p photoelectron holograms, we directly reconstructed atomic images of the cleaved surface of a bimetal-intercalated graphite superconductor, (Ca, K)C8, which differed substantially from the expected bulk crystal structure based on x-ray diffraction (XRD) measurements. Graphene atomic images were collected in the in-plane cross sections of the layers 3.3 Å and 5.7 Å above the photoelectron emitter C atom and the stacking structures were determined as AB- and AA-type, respectively. The intercalant metal atom layer was found between two AA-stacked graphenes. The K atomic image revealing 2 × 2 periodicity, occupying every second centre site of C hexagonal columns, was reconstructed, and the Ca 2p peak intensity in the photoelectron spectra of (Ca, K)C8 from the cleaved surface was less than a few hundredths of the K 2p peak intensity. These observations indicated that cleavage preferentially occurs at the KC8 layers containing no Ca atoms. PMID:27811975

Synthesis and characterization of [4-(2,4-dichlorophenoxybutyrate)-zinc layered hydroxide] nanohybrid

NASA Astrophysics Data System (ADS)

Hussein, Mohd Zobir; Hashim, Norhayati; Yahaya, Asmah Hj.; Zainal, Zulkarnain

2010-05-01

A new layered organic-inorganic nanohybrid material in which an agrochemical, 4-(2,4-dichlorophenoxy)butyrate (DPBA) is intercalated into inorganic interlayers of zinc layered hydroxide (ZLH) was synthesized by direct reaction of aqueous DPBA solution with zinc oxide. The resulting nanohybrid is composed of the organic moieties, DPBA sandwiched between ZLH inorganic interlayers. The nanohybrid afforded well ordered crystalline layered structure, a basal spacing of 29.6 Å, 23.5% carbon (w/w) and 47.9% (w/w) loading of DPBA. FTIR study shows that the absorption bands of the resulting nanohybrid composed the FTIR characteristics of both the DPBA and ZLH which further confirmed the intercalation episode. The intercalated organic moiety in the form of nanohybrid is thermally more stable than its sodium salt. Scanning electron micrograph shows the ZnO precursor has very fine granular structure and transformed into a flake-like when the nanohybrid is formed. This work shows that the nanohybrid of DPBA-ZLH can be synthesized using simple, direct reaction of ZnO and DPBA under aqueous environment for the formation of a new generation of agrochemical.

Synthesis of kaolinite-filled EPDM rubber composites by solution intercalation: structural characterization and studies on mechanical properties

NASA Astrophysics Data System (ADS)

Ginil Mon, S.; Jaya Vinse Ruban, Y.; Vetha Roy, D.

2011-09-01

In the large field of nanotechnology, polymer matrix-based nanocomposites have become a prominent area of current research and development. Exfoliated clay-based nanocomposites have dominated the polymer world with excellent characteristics. EPDM rubber composites have been synthesized by solution-intercalation using the easily available kaolinite as filler. The composite structure has been elucidated by X-ray diffraction (XRD), Fourier transform IR, and scanning electron microscope studies. The molecular level dispersion of clay layers has been verified by the disappearance of basal XRD peak of kaolinite in the EPDM/kaolinite composites. The mechanical properties showed significant improvement of EPDM/kaolinite composites with respect to neat EPDM.

Transformers: the changing phases of low-dimensional vanadium oxide bronzes.

PubMed

Marley, Peter M; Horrocks, Gregory A; Pelcher, Kate E; Banerjee, Sarbajit

2015-03-28

In this feature article, we explore the electronic and structural phase transformations of ternary vanadium oxides with the composition MxV2O5 where M is an intercalated cation. The periodic arrays of intercalated cations ordered along quasi-1D tunnels or layered between 2D sheets of the V2O5 framework induce partial reduction of the framework vanadium atoms giving rise to charge ordering patterns that are specific to the metal M and stoichiometry x. This periodic charge ordering makes these materials remarkably versatile platforms for studying electron correlation and underpins the manifestation of phenomena such as colossal metal-insulator transitions, quantized charge corrals, and superconductivity. We describe current mechanistic understanding of these emergent phenomena with a particular emphasis on the benefits derived from scaling these materials to nanostructured dimensions wherein precise ordering of cations can be obtained and phase relationships can be derived that are entirely inaccessible in the bulk. In particular, structural transformations induced by intercalation are dramatically accelerated due to the shorter diffusion path lengths at nanometer-sized dimensions, which cause a dramatic reduction of kinetic barriers to phase transformations and facilitate interconversion between the different frameworks. We conclude by summarizing numerous technological applications that have become feasible due to recent advances in controlling the structural chemistry and both electronic and structural phase transitions in these versatile frameworks.

Atomic structures and electronic properties of 2H-NbSe2: The impact of Ti doping

NASA Astrophysics Data System (ADS)

Li, Hongping; Chen, Lin; Zhang, Kun; Liang, Jiaqing; Tang, Hua; Li, Changsheng; Liu, Xiaojuan; Meng, Jian; Wang, Zhongchang

2014-09-01

Layered transition metal dichalcogenides have aroused renewed interest as electronic materials, yet their electronic performances could be modified by chemical doping. Here, we perform a systematic first-principles calculation to investigate the effect of Ti doping on atomic structure and electronic properties of the 2H-NbSe2. We consider a total of three possible Ti-doping models and find that both the substitution and intercalated models are chemically preferred with the intercalation model being more favorable than the substitution one. Structural analyses reveal a slight lattice distortion triggered by Ti doping, but the original structure of 2H-NbSe2 is maintained. We also observe an expansion of c axis in the substituted model, which is attributed to the reduced van der Waals interaction arising from the increased Se-Se bond length. Our calculations also predict that the electron transport properties can be enhanced by the Ti doping, especially for the Ti-intercalated 2H-NbSe2, which should be beneficial for the realization of superconductivity. Furthermore, the covalence element is found in the Ti-Se bonds, which is ascribed to the hybridization of Ti 3d and Se 4p orbitals. The findings indicate that doping of transition metals can be regarded as a useful way to tailor electronic states so as to improve electron transport properties of 2H-NbSe2.

Structures spatiales localisées dans un oscillateur paramétrique optique (OPO)

NASA Astrophysics Data System (ADS)

Coulibaly, S.; Durniak, C.; Taki, M.

2004-11-01

La prise en compte du caractère non uniforme du pompage optique dans l'étude linéaire et faiblement non linéaire d'un OPO dégénéré (DOPO) a permis de mettre en évidence la discrétisation du seuil et l'existence de structures spatiales localisées de type Hermite-Gauss. L'évolution spatio-temporelle du signal en sortie est quant à elle gouvernée par l'équation de Ginzburg-Landau réelle dont les coefficients dépendent des variables d'espace.

Probing Atomic, Electronic, and Optical Structures of Nanoparticle Photocatalysts Using Fast Electrons

NASA Astrophysics Data System (ADS)

Liu, Qianlang

Graphene has attracted great interest in many fields due to its outstanding electronic and chemical properties. Among them, its surface inertness and high thermal stability makes graphene a promising candidate as a protective material for transition metal surfaces. Recent studies show, however, that small molecules, such as O2, CO and H2O, intercalate between a graphene film and a metal substrate at particular temperatures. The intercalation of O2 between graphene and Ru(0001) is studied with 3 keV helium ion scattering and low energy electron diffraction. It is shown that O2 intercalates between the graphene and the Ru(0001) substrate at a temperature of 650 K and does not adsorb onto the graphene surface. Nevertheless, the graphene layer efficiently avoids both intercalation and adsorption of oxygen at room temperature. It is also found that the intercalated oxygen thermally desorbs from the surface after it is heated to 800 K. Such a desorption is not, however, observed for oxygen dissociatively adsorbed on a bare Ru(0001) surface until 1200 K. It is thus inferred that the oxygen intercalated between graphene and Ru(0001) is in a molecular form. In addition, part of the graphene overlayer is etched by a chemical reaction during the thermal desorption of oxygen. The role of the defects on the graphene layer is also studied. Defects are introduced by 50 eV Ar+ sputtering, which creates single vacancies with a quick sputtering or larger open areas of substrate following a prolonged sputtering. It is found that oxygen molecularly adsorbs at single carbon vacancies even at room temperature, which does not occur on a complete graphene layer. Following post-annealing to 600 K, it is observed that such adsorbed oxygen diffuses to become intercalated between graphene and Ru(0001). Oxygen dissociatively adsorbs in the large open areas of exposed substrate by forming strong oxygen-metal bonds. It is also found that the presence of defects facilitates the intercalation of oxygen and improves the etching efficiency of the graphene during the desorption of oxygen.

NMR solution structure of an N2-guanine DNA adduct derived from the potent tumorigen dibenzo[a,l]pyrene: Intercalation from the minor groove with ruptured Watson-Crick base pairing

PubMed Central

Tang, Yijin; Liu, Zhi; Ding, Shuang; Lin, Chin H.; Cai, Yuqin; Rodriguez, Fabian A.; Sayer, Jane M.; Jerina, Donald M.; Amin, Shantu; Broyde, Suse; Geacintov, Nicholas E.

2012-01-01

The most potent tumorigen identified among the polycyclic aromatic hydrocarbons (PAH) is the non-planar fjord region dibenzo[a,l]pyrene (DB[a,l]P). It is metabolically activated in vivo through the widely-studied diol epoxide (DE) pathway to form covalent adducts with DNA bases, predominantly guanine and adenine. The (+)-11S,12R,13R,14S DE enantiomer forms adducts via its C14-position with the exocyclic amino group of guanine. Here, we present the first NMR solution structure of a DB[a,l]P-derived adduct, the 14R (+)-trans-anti-DB[a,l]P–N2-dG (DB[a,l]P-dG) lesion in double-stranded DNA. In contrast to the stereochemically identical benzo[a]pyrene-derived N2-dG adduct (B[a]P-dG) in which the B[a]P rings reside in the B-DNA minor groove on the 3’-side of the modifed deoxyguanosine, in the DB[a,l]P-derived adduct the DB[a,l]P rings intercalate into the duplex on the 3’-side of the modified base from the sterically crowded minor groove. Watson-Crick base pairing of the modified guanine with the partner cytosine is broken, but these bases retain some stacking with the bulky DB[a,l]P ring system. This new theme in PAH DE - DNA adduct conformation differs from: (1) the classical intercalation motif where Watson-Crick base-pairing is intact at the lesion site, and (2) the base-displaced intercalation motif in which the damaged base and its partner are extruded from the helix . The structural considerations that lead to the intercalated conformation of the DB[a,l]P-dG lesion in contrast to the minor groove alignment of the B[a]P-dG adduct, and the implications of the DB[a,l]P-dG conformational motif for the recognition of such DNA lesions by the human nucleotide excision repair apparatus, are discussed. PMID:23121427

Nuclear magnetic resonance solution structure of an N(2)-guanine DNA adduct derived from the potent tumorigen dibenzo[a,l]pyrene: intercalation from the minor groove with ruptured Watson-Crick base pairing.

PubMed

Tang, Yijin; Liu, Zhi; Ding, Shuang; Lin, Chin H; Cai, Yuqin; Rodriguez, Fabian A; Sayer, Jane M; Jerina, Donald M; Amin, Shantu; Broyde, Suse; Geacintov, Nicholas E

2012-12-04

The most potent tumorigen identified among the polycyclic aromatic hydrocarbons (PAH) is the nonplanar fjord region dibenzo[a,l]pyrene (DB[a,l]P). It is metabolically activated in vivo through the widely studied diol epoxide (DE) pathway to form covalent adducts with DNA bases, predominantly guanine and adenine. The (+)-11S,12R,13R,14S DE enantiomer forms adducts via its C14 position with the exocyclic amino group of guanine. Here, we present the first nuclear magnetic resonance solution structure of a DB[a,l]P-derived adduct, the 14R-(+)-trans-anti-DB[a,l]P-N(2)-dG (DB[a,l]P-dG) lesion in double-stranded DNA. In contrast to the stereochemically identical benzo[a]pyrene-derived N(2)-dG adduct (B[a]P-dG) in which the B[a]P rings reside in the B-DNA minor groove on the 3'-side of the modifed deoxyguanosine, in the DB[a,l]P-derived adduct the DB[a,l]P rings intercalate into the duplex on the 3'-side of the modified base from the sterically crowded minor groove. Watson-Crick base pairing of the modified guanine with the partner cytosine is broken, but these bases retain some stacking with the bulky DB[a,l]P ring system. This new theme in PAH DE-DNA adduct conformation differs from (1) the classical intercalation motif in which Watson-Crick base pairing is intact at the lesion site and (2) the base-displaced intercalation motif in which the damaged base and its partner are extruded from the helix. The structural considerations that lead to the intercalated conformation of the DB[a,l]P-dG lesion in contrast to the minor groove alignment of the B[a]P-dG adduct, and the implications of the DB[a,l]P-dG conformational motif for the recognition of such DNA lesions by the human nucleotide excision repair apparatus, are discussed.

Elaboration et caracterisation de nanocomposites polyethylene/montmorillonite

NASA Astrophysics Data System (ADS)

Stoeffler, Karen

This research project consists in preparing polyethylene/montmorillonite nanocomposites for film packaging applications. Montmorillonite is a natural clay with an exceptional aspect ratio. In recent years, its incorporation in polymer matrices has attracted great interest. The pioneer work from Toyota on polyamide-6/montmorillonite composites has shown that it was possible to disperse the clay at a nanometric scale. Such a structure, so-called exfoliated, leads to a significant increase in mechanical, barrier and fire retardant properties, even at low volumetric fractions of clay. This allows a valorization of the polymeric material at moderate cost. Due to its high polarity, montmorilloite exfoliation in polymeric matrices is problematic. In the particular case of polyolefin matrices, the platelets dispersion remains limited: most frequently, the composites obtained exhibit conventional structures (microcomposites) or intercalated structures. To solve this problem, two techniques are commonly employed: the surface treatment of the clay, which allows the expansion of the interfoliar gallery while increasing the affinity between the clay and the polymer, and the use of a polar compatibilizing agent (grafted polyolefin). The first part of this thesis deals with the preparation and the characterization of highly thermally stable organophilic montmorillonites. Commercial organophilic montmorillonites are treated with quaternary ammonium intercalating agents. However, those intercalating agents present a poor thermal stability and are susceptible to decompose upon processing, thus affecting the clay dispersion and the final properties of the nanocomposites. In this work, it was proposed to modify the clay with alkyl pyridinium, alkyl imidazolium and alkyl phosphonium intercalating agents, which are more stable than ammonium based cations. Organophilic montmorillonites with enhanced thermal stabilites compared to commercial organoclays (+20°C to +70°C) were prepared. The effect of the chemical structure of the intercalating agent on the capacity of the organoclay to be dispersed in polyethylene matrices was analyzed. In addition, the influence of the dispersion on the thermal stability of the nanocomposites prepared is discussed. In a second part, the effect of the compatibilizing agent characteristics on the quality of the clay dispersion in polyethylene/montmorillonite nanocomposites was analyzed. The mechanical properties and the oxygen permeability of the nanocomposites were evaluated and related to the level of clay delamination and to the strength of the polymer/clay interface, which was evaluated through surface tension measurements.

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Daojin; Cai, Zhao; Bi, Yongmin

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Temperature dependent local atomic displacements in ammonia intercalated iron selenide superconductor

NASA Astrophysics Data System (ADS)

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.

2016-06-01

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.

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

DOE PAGES

Zhou, Daojin; Cai, Zhao; Bi, Yongmin; ...

2018-02-02

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Binding of DNA-binding alkaloids berberine and palmatine to tRNA and comparison to ethidium: Spectroscopic and molecular modeling studies

NASA Astrophysics Data System (ADS)

Islam, Md. Maidul; Pandya, Prateek; Chowdhury, Sebanti Roy; Kumar, Surat; Kumar, Gopinatha Suresh

2008-11-01

The interaction of two natural protoberberine plant alkaloids berberine and palmatine with tRNA phe was studied using various biophysical techniques and molecular modeling and the data were compared with the binding of the classical DNA intercalator, ethidium. Circular dichroic studies revealed that the tRNA conformation was moderately perturbed on binding of the alkaloids. The cooperative binding of both the alkaloids and ethidium to tRNA was revealed from absorbance and fluorescence studies. Fluorescence quenching studies advanced a conclusion that while berberine and palmatine are partially intercalated, ethidium is fully intercalated on the tRNA molecule. The binding of the alkaloids as well as ethidium stabilized the tRNA melting, and the binding constant evaluated from the averaged optical melting temperature data was in agreement with fluorescence spectral-binding data. Differential scanning calorimetry revealed that the tRNA melting showed three close transitions that were affected on binding of these small molecules. Molecular docking calculations performed showed the preferred regions of binding of these small molecules on the tRNA. Taken together, the results suggest that the binding of the alkaloids berberine and palmatine on the tRNA structure appears to be mostly by partial intercalation while ethidium intercalates fully on the tRNA. These results further advance our knowledge on the molecular aspects on the interaction of these alkaloids to tRNA.

Effects of Applied Potential and Water Intercalation on the Surface Chemistry of Ti 2C and Mo 2C MXenes

DOE PAGES

Fredrickson, Kurt D.; Anasori, Babak; Seh, Zhi Wei; ...

2016-12-09

Here, two-dimensional transition metal carbides and nitrides, also known as MXenes, represent an attractive class of materials for a multitude of electrochemical and other applications. While single sheets of MXenes have been widely studied theoretically, there have been much fewer studies on layered bulk MXenes, which are more representative of multi- or few-layer MXenes used in actual applications. Herein, we investigate the structural and electronic effects of water intercalation, multiple functional groups and applied potential on layered bulk Ti 2C and Mo 2C MXenes using density functional theory. The out-of plane lattice parameter, c, was found to vary significantly withmore » the functional group, and is greatly increased upon intercalation of water. Experimental results confirm the change in lattice constant due to addition or removal of intercalated water. Under zero applied potential, both Ti 2C and Mo 2C were found to be functionalized by one monolayer of O; bare MXenes were never found to be stable, regardless of the applied potential. Applying a potential changed the adsorbate coverage, changing the systems from O covered to H covered at negative potentials and, in some cases, giving rise to a metal–insulator transition. Understanding of the effects of surface functionalization and water intercalation of MXenes provides a better insight of their use for catalytic and electronic applications.« less

Synthesis and characterization of Mg-Al-layered double hydroxides intercalated with cubane-1,4-dicarboxylate anions.

PubMed

Rezvani, Zolfaghar; Arjomandi Rad, Farzad; Khodam, Fatemeh

2015-01-21

In the present work, Mg2Al-layered double hydroxide (LDH) intercalated with cubane-1,4-dicarboxylate anions was prepared from the reaction of solutions of Mg(ii) and Al(iii) nitrate salts with an alkaline solution of cubane-1,4-dicarboxylic acid by using the coprecipitation method. The successful preparation of a nanohybrid of cubane-1,4-dicarboxylate(cubane-dc) anions with LDH was confirmed by powder X-ray diffraction, FTIR spectroscopy and thermal gravimetric analysis (TGA). The increase in the basal spacing of LDHs from 8.67 Å to 13.40 Å shows that cubane-dc anions were successfully incorporated into the interlayer space. Thermogravimetric analyses confirm that the thermal stability of the intercalated cubane-dc anions is greater than that of the pure form before intercalation because of host-guest interactions involving hydrogen bonds. The interlayer structure, hydrogen bonding, and subsequent distension of LDH compounds containing cubane-dc anions were shown by molecular simulation. The RDF (radial distribution function), mean square displacement (MSD), and self-diffusion coefficient were calculated using the trajectory files on the basis of molecular dynamics (MD) simulations, and the results indicated that the cubane-dc anions were more stable when intercalated into the LDH layers. A good agreement was obtained between calculated and measured X-ray diffraction patterns and between experimental and calculated basal spacings.

Intercalation of sulfonated melamine formaldehyde polycondensates into a hydrocalumite LDH structure

NASA Astrophysics Data System (ADS)

von Hoessle, F.; Plank, J.; Leroux, F.

2015-05-01

A series of sulfonated melamine formaldehyde (SMF) polycondensates possessing different anionic charge amounts and molecular weights was synthesized and incorporated into a hydrocalumite type layered double hydroxide structure using the rehydration method. For this purpose, tricalcium aluminate was dispersed in water and hydrated in the presence of these polymers. Defined inorganic-organic hybrid materials were obtained as reaction products. All SMF polymers tested intercalated readily into the hydrocalumite structure, independent of their different molecular weights (chain lengths) and anionic charge amounts. X-ray diffraction revealed typical patterns for weakly ordered, highly polymer loaded LDH materials which was confirmed via elemental analysis and thermogravimetry. IR spectroscopy suggests that the SMF polymers are interleaved between the [Ca2Al(OH)6]+ main sheets via electrostatic interaction, and that no chemical bond between the host matrix and the guest anion is formed. The SMF polymers well ensconced within the LDH structure exhibit significantly slower thermal degradation.

Structure and dynamics of proflavine association around DNA.

PubMed

Sasikala, Wilbee D; Mukherjee, Arnab

2016-04-21

Proflavine is a small molecule that intercalates into DNA and, thereby, acts as an anticancer agent. Intercalation of proflavine is shown to be a two-step process in which the first step is believed to be the formation of a pre-intercalative outside bound state. Experimental studies so far have been unable to capture the nature of the outside bound state. However, the sub-millisecond timescale observed in fluorescence kinetic experiments is often attributed to the binding of proflavine outside of DNA. Here, we have performed molecular dynamics simulations with multiple proflavine molecules to study the structure and dynamics of the formation of the outside bound state of DNA at different ion concentrations. We observed that the timescale of the outside bound state formation is, at least, five orders of magnitude faster (in nanoseconds) than the experimentally reported timescale (sub-milliseconds) attributed to binding outside DNA. Moreover, we also observed the stacked arrangement of proflavine all around DNA, which is different from the experimentally predicted stacking arrangement perpendicular to the helical axis of DNA in the close vicinity of the phosphate groups. This study, therefore, provides insight into the molecular structure and dynamics of the pre-intercalative outside bound state and will help in understanding the overall intercalation mechanism.

Monolayer atomic crystal molecular superlattices.

PubMed

Wang, Chen; He, Qiyuan; Halim, Udayabagya; Liu, Yuanyue; Zhu, Enbo; Lin, Zhaoyang; Xiao, Hai; Duan, Xidong; Feng, Ziying; Cheng, Rui; Weiss, Nathan O; Ye, Guojun; Huang, Yun-Chiao; Wu, Hao; Cheng, Hung-Chieh; Shakir, Imran; Liao, Lei; Chen, Xianhui; Goddard, William A; Huang, Yu; Duan, Xiangfeng

2018-03-07

Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 10 7 , along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

Monolayer atomic crystal molecular superlattices

NASA Astrophysics Data System (ADS)

Wang, Chen; He, Qiyuan; Halim, Udayabagya; Liu, Yuanyue; Zhu, Enbo; Lin, Zhaoyang; Xiao, Hai; Duan, Xidong; Feng, Ziying; Cheng, Rui; Weiss, Nathan O.; Ye, Guojun; Huang, Yun-Chiao; Wu, Hao; Cheng, Hung-Chieh; Shakir, Imran; Liao, Lei; Chen, Xianhui; Goddard, William A., III; Huang, Yu; Duan, Xiangfeng

2018-03-01

Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 107, along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

Microstructural response of variably hydrated Ca-rich montmorillonite to supercritical CO2.

PubMed

Lee, Mal-Soon; McGrail, B Peter; Glezakou, Vassiliki-Alexandra

2014-01-01

First-principles molecular dynamics simulations were carried out to explore the mechanistic and thermodynamic ramifications of the exposure of variably hydrated Ca-rich montmorillonites to supercritical CO2 and CO2-SO2 mixtures under geologic storage conditions. In sub- to single-hydrated systems (≤ 1W), CO2 intercalation causes interlamellar expansion of 8-12%, while systems transitioning to 2W may undergo contraction (∼ 7%) or remain almost unchanged. When compared to ∼2W hydration state, structural analysis of the ≤ 1W systems, reveals more Ca-CO2 contacts and partial transition to vertically confined CO2 molecules. Infrared spectra and projected vibrational frequency analysis imply that intercalated Ca-bound CO2 are vibrationally constrained and contribute to the higher frequencies of the asymmetric stretch band. Reduced diffusion coefficients of intercalated H2O and CO2 (10(-6)-10(-7) cm(2)/s) indicate that Ca-montmorillonites in ∼ 1W hydration states can be more efficient in capturing CO2. Simulations including SO2 imply that ∼ 0.66 mmol SO2/g clay can be intercalated without other significant structural changes. SO2 is likely to divert H2O away from the cations, promoting Ca-CO2 interactions and CO2 capture by further reducing CO2 diffusion (10(-8) cm(2)/s). Vibrational bands at ∼ 1267 or 1155 cm(-1) may be used to identify the chemical state (oxidation states +4 or +6, respectively) and the fate of sulfur contaminants.

Graphite fiber intercalation: Dynamics of the bromine intercalation process

NASA Technical Reports Server (NTRS)

Jaworske, D. A.; Zinolabedini, R.

1985-01-01

The resistance of pitch-based graphite fibers was monitored, in situ, during a series of bromine intercalation experiments. The threshold pressure for the bromine intercalation of pitch-based fibers was estimated to be 102 torr. When the bromine atmosphere was removed from the reaction chamber, the resistivity of the intercalated graphite fibers increased consistently. This increase was attributed to loss of bromine from the perimeter of the fiber. The loss was confirmed by mapping the bromine concentration across the diameter of single intercalated fibers with either energy dispersive spectroscopy or scanning Auger microscopy. A statistical study comparing fibers intercalated in bromine vapor with fibers intercalated in bromine liquid showed that similar products were obtained with both methods of intercalation.

Structural and Kinetic Properties of Graphite Intercalation Compounds

DTIC Science & Technology

1982-08-21

the case of FeCI3 , and Dowel2 for Br2, HNO3 and PdC 2 have investigated rates of intercalation to determine diffusion coefficients. Bardhan et al.18...Chim. 21, 1312 (1954). 17. T. Sasa, Y. Takahashi and T. Mukaibo, Carbon 9, 407 (1971). 18. K. K. Bardhan and D. D. L. Chung, Carbon 18, 313 (1980). 19...S. H. Anderson and D. D. L. Chung, Ext. Abst. Program -- Bienn. Conf. Carbon 15, 361 (1981). 20. K. K. Bardhan and D. D. L. Chung, Carbon 18, 303

Fluctuations Magnetiques des Gaz D'electrons Bidimensionnels: Application AU Compose Supraconducteur LANTHANE(2-X) Strontium(x) Cuivre OXYGENE(4)

NASA Astrophysics Data System (ADS)

Benard, Pierre

Nous presentons une etude des fluctuations magnetiques de la phase normale de l'oxyde de cuivre supraconducteur La_{2-x}Sr _{x}CuO_4 . Le compose est modelise par le Hamiltonien de Hubbard bidimensionnel avec un terme de saut vers les deuxiemes voisins (modele tt'U). Le modele est etudie en utilisant l'approximation de la GRPA (Generalized Random Phase Approximation) et en incluant les effets de la renormalisation de l'interaction de Hubbard par les diagrammes de Brueckner-Kanamori. Dans l'approche presentee dans ce travail, les maximums du facteur de structure magnetique observes par les experiences de diffusion de neutrons sont associes aux anomalies 2k _{F} de reseau du facteur de structure des gaz d'electrons bidimensionnels sans interaction. Ces anomalies proviennent de la diffusion entre particules situees a des points de la surface de Fermi ou les vitesses de Fermi sont tangentes, et conduisent a des divergences dont la nature depend de la geometrie de la surface de Fermi au voisinage de ces points. Ces resultats sont ensuite appliques au modele tt'U, dont le modele de Hubbard usuel tU est un cas particulier. Dans la majorite des cas, les interactions ne determinent pas la position des maximums du facteur de structure. Le role de l'interaction est d'augmenter l'intensite des structures du facteur de structure magnetique associees a l'instabilite magnetique du systeme. Ces structures sont souvent deja presentes dans la partie imaginaire de la susceptibilite sans interaction. Le rapport d'intensite entre les maximums absolus et les autres structures du facteur de structure magnetique permet de determiner le rapport U_ {rn}/U_{c} qui mesure la proximite d'une instabilite magnetique. Le diagramme de phase est ensuite etudie afin de delimiter la plage de validite de l'approximation. Apres avoir discute des modes collectifs et de l'effet d'une partie imaginaire non-nulle de la self-energie, l'origine de l'echelle d'energie des fluctuations magnetiques est examinee. Il est ensuite demontre que le modele a trois bandes predit les memes resultats pour la position des structures du facteur de structure magnetique que le modele a une bande, dans la limite ou l'hybridation des orbitales des atomes d'oxygene des plans Cu-O_2 et l'amplitude de sauts vers les seconds voisins sont nulles. Il est de plus constate que l'effet de l'hybridation des orbitales des atomes d'oxygene est bien modelise par le terme de saut vers les seconds voisins. Meme si ils decrivent correctement le comportement qualitatif des maximums du facteur de structure magnetique, les modeles a trois bandes et a une bande ne permettent pas d'obtenir une position de ces structures conforme avec les mesures experimentales, si on suppose que la bande est rigide, c'est-a-dire que les parametres du Hamiltonien sont independants de la concentration de strontium. Ceci peut etre cause par la dependance des parametres du Hamiltonien sur la concentration de strontium. Finalement, les resultats sont compares avec les experiences de diffusion de neutrons et les autres theories, en particulier celles de Littlewood et al. (1993) et de Q. Si et al. (1993). La comparaison avec les resultats experimentaux pour le compose de lanthane suggere que le liquide de Fermi possede une surface de Fermi disjointe, et qu'il est situe pres d'une instabilite magnetique incommensurable.

Retention of contaminants Cd and Hg adsorbed and intercalated in aluminosilicate clays: A first principles study

NASA Astrophysics Data System (ADS)

Crasto de Lima, F. D.; Miwa, R. H.; Miranda, Caetano R.

2017-11-01

Layered clay materials have been used to incorporate transition metal (TM) contaminants. Based on first-principles calculations, we have examined the energetic stability and the electronic properties due to the incorporation of Cd and Hg in layered clay materials, kaolinite (KAO) and pyrophyllite (PYR). The TM can be (i) adsorbed on the clay surface as well as (ii) intercalated between the clay layers. For the intercalated case, the contaminant incorporation rate can be optimized by controlling the interlayer spacing of the clay, namely, pillared clays. Our total energy results reveal that the incorporation of the TMs can be maximized through a suitable tuning of vertical distance between the clay layers. Based on the calculated TM/clay binding energies and the Langmuir absorption model, we estimate the concentrations of the TMs. Further kinetic properties have been examined by calculating the activation energies, where we found energy barriers of ˜20 and ˜130 meV for adsorbed and intercalated cases, respectively. The adsorption and intercalation of ionized TM adatoms were also considered within the deprotonated KAO surface. This also leads to an optimal interlayer distance which maximizes the TM incorporation rate. By mapping the total charge transfers at the TM/clay interface, we identify a net electronic charge transfer from the TM adatoms to the topmost clay surface layer. The effect of such a charge transfer on the electronic structure of the clay (host) has been examined through a set of X-ray absorption near edge structure (XANES) simulations, characterizing the changes of the XANES spectra upon the presence of the contaminants. Finally, for the pillared clays, we quantify the Cd and Hg K-edge energy shifts of the TMs as a function of the interlayer distance between the clay layers and the Al K-edge spectra for the pristine and pillared clays.

Structure and dynamics in low-dimensional guest host solids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fischer, J.

1991-04-01

This progress report presents results from work during the period of June 1, 1990 through May 31st, 1991. Topics discussed include instrumentation, publications, and personnel. Work areas discussed include: pressure-induced transitions in Li- and Ag-TiS{sub 2}, hyper-dense superconducting GIC's, temperature-dependent x-ray structure of (CH){sub x} and (CH){sub 2{sup x}}:analogies to rotator phases in short-chain alkanes, trans-(CH){sub x} at high'' pressure, broken symmetries'' in polymer intercalation channel lattices, high-resolution study of conductivity and cell potential vs. concentration in K-doped (CH){sub x}, new'' doped (CH){sub x} phases: ternary compounds and amorphous'' intercalation compounds, and vibrational density states from inelastic neutron scattering. (JF).

Structure of the USP15 N-terminal domains: a β-hairpin mediates close association between the DUSP and UBL domains.

PubMed

Harper, Stephen; Besong, Tabot M D; Emsley, Jonas; Scott, David J; Dreveny, Ingrid

2011-09-20

Ubiquitin specific protease 15 (USP15) functions in COP9 signalosome mediated regulation of protein degradation and cellular signaling through catalyzing the ubiquitin deconjugation reaction of a discrete number of substrates. It influences the stability of adenomatous polyposis coli, IκBα, caspase-3, and the human papillomavirus type 16 E6. USP15 forms a subfamily with USP4 and USP11 related through a shared presence of N-terminal "domain present in ubiquitin specific proteases" (DUSP) and "ubiquitin-like" (UBL) domains (DU subfamily). Here we report the 1.5 Å resolution crystal structure of the human USP15 N-terminal domains revealing a 80 Å elongated arrangement with the DU domains aligned in tandem. This architecture is generated through formation of a defined interface that is dominated by an intervening β-hairpin structure (DU finger) that engages in an intricate hydrogen-bonding network between the domains. The UBL domain is closely related to ubiquitin among β-grasp folds but is characterized by the presence of longer loop regions and different surface characteristics, indicating that this domain is unlikely to act as ubiquitin mimic. Comparison with the related murine USP4 DUSP-UBL crystal structure reveals that the main DU interdomain contacts are conserved. Analytical ultracentrifugation, small-angle X-ray scattering, and gel filtration experiments revealed that USP15 DU is monomeric in solution. Our data provide a framework to advance study of the structure and function of the DU subfamily. © 2011 American Chemical Society

Theoretical Investigation of oxides for batteries and fuel cell applications

NASA Astrophysics Data System (ADS)

Ganesh, Panchapakesan; Lubimtsev, Andrew A.; Balachandran, Janakiraman

I will present theoretical studies of Li-ion and proton-conducting oxides using a combination of theory and computations that involve Density Functional Theory based atomistic modeling, cluster-expansion based studies, global optimization, high-throughput computations and machine learning based investigation of ionic transport in oxide materials. In Li-ion intercalated oxides, we explain the experimentally observed (Nature Materials 12, 518-522 (2013)) 'intercalation pseudocapacitance' phenomenon, and explain why Nb2O5 is special to show this behavior when Li-ions are intercalated (J. Mater. Chem. A, 2013,1, 14951-14956), but not when Na-ions are used. In addition, we explore Li-ion intercalation theoretically in VO2 (B) phase, which is somewhat structurally similar to Nb2O5 and predict an interesting role of site-trapping on the voltage and capacity of the material, validated by ongoing experiments. Computations of proton conducting oxides explain why Y-doped BaZrO3 , one of the fastest proton conducting oxide, shows a decrease in conductivity above 20% Y-doping. Further, using high throughput computations and machine learning tools we discover general principles to improve proton conductivity. Acknowledgements: LDRD at ORNL and CNMS at ORNL

Anthraquinones quinizarin and danthron unwind negatively supercoiled DNA and lengthen linear DNA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Verebová, Valéria; Adamcik, Jozef; Danko, Patrik

2014-01-31

Highlights: • Anthraquinones quinizarin and danthron unwind negatively supercoiled DNA. • Anthraquinones quinizarin and danthron lengthen linear DNA. • Anthraquinones quinizarin and danthron possess middle binding affinity to DNA. • Anthraquinones quinizarin and danthron interact with DNA by intercalating mode. - Abstract: The intercalating drugs possess a planar aromatic chromophore unit by which they insert between DNA bases causing the distortion of classical B-DNA form. The planar tricyclic structure of anthraquinones belongs to the group of chromophore units and enables anthraquinones to bind to DNA by intercalating mode. The interactions of simple derivatives of anthraquinone, quinizarin (1,4-dihydroxyanthraquinone) and danthron (1,8-dihydroxyanthraquinone),more » with negatively supercoiled and linear DNA were investigated using a combination of the electrophoretic methods, fluorescence spectrophotometry and single molecule technique an atomic force microscopy. The detection of the topological change of negatively supercoiled plasmid DNA, unwinding of negatively supercoiled DNA, corresponding to appearance of DNA topoisomers with the low superhelicity and an increase of the contour length of linear DNA in the presence of quinizarin and danthron indicate the binding of both anthraquinones to DNA by intercalating mode.« less

Nucleation and growth kinetics for intercalated islands during deposition on layered materials with isolated pointlike surface defects

DOE PAGES

Han, Yong; Lii-Rosales, A.; Zhou, Y.; ...

2017-10-13

Theory and stochastic lattice-gas modeling is developed for the formation of intercalated metal islands in the gallery between the top layer and the underlying layer at the surface of layered materials. Our model for this process involves deposition of atoms, some fraction of which then enter the gallery through well-separated pointlike defects in the top layer. Subsequently, these atoms diffuse within the subsurface gallery leading to nucleation and growth of intercalated islands nearby the defect point source. For the case of a single point defect, continuum diffusion equation analysis provides insight into the nucleation kinetics. However, complementary tailored lattice-gas modelingmore » produces a more comprehensive and quantitative characterization. We analyze the large spread in nucleation times and positions relative to the defect for the first nucleated island. We also consider the formation of subsequent islands and the evolution of island growth shapes. The shapes reflect in part our natural adoption of a hexagonal close-packed island structure. As a result, motivation and support for the model is provided by scanning tunneling microscopy observations of the formation of intercalated metal islands in highly-ordered pyrolytic graphite at higher temperatures.« less

Interface confined hydrogen evolution reaction in zero valent metal nanoparticles-intercalated molybdenum disulfide

PubMed Central

Chen, Zhongxin; Leng, Kai; Zhao, Xiaoxu; Malkhandi, Souradip; Tang, Wei; Tian, Bingbing; Dong, Lei; Zheng, Lirong; Lin, Ming; Yeo, Boon Siang; Loh, Kian Ping

2017-01-01

Interface confined reactions, which can modulate the bonding of reactants with catalytic centres and influence the rate of the mass transport from bulk solution, have emerged as a viable strategy for achieving highly stable and selective catalysis. Here we demonstrate that 1T′-enriched lithiated molybdenum disulfide is a highly powerful reducing agent, which can be exploited for the in-situ reduction of metal ions within the inner planes of lithiated molybdenum disulfide to form a zero valent metal-intercalated molybdenum disulfide. The confinement of platinum nanoparticles within the molybdenum disulfide layered structure leads to enhanced hydrogen evolution reaction activity and stability compared to catalysts dispersed on carbon support. In particular, the inner platinum surface is accessible to charged species like proton and metal ions, while blocking poisoning by larger sized pollutants or neutral molecules. This points a way forward for using bulk intercalated compounds for energy related applications. PMID:28230105

The structure of graphene oxide membranes in liquid water, ethanol and water-ethanol mixtures

NASA Astrophysics Data System (ADS)

Talyzin, Alexandr V.; Hausmaninger, Tomas; You, Shujie; Szabó, Tamás

2013-12-01

The structure of graphene oxide (GO) membranes was studied in situ in liquid solvents using synchrotron radiation X-ray diffraction in a broad temperature interval. GO membranes are hydrated by water similarly to precursor graphite oxide powders but intercalation of alcohols is strongly hindered, which explains why the GO membranes are permeated by water and not by ethanol. Insertion of ethanol into the membrane structure is limited to only one monolayer in the whole studied temperature range, in contrast to precursor graphite oxide powders, which are intercalated with up to two ethanol monolayers (Brodie) and four ethanol monolayers (Hummers). As a result, GO membranes demonstrate the absence of ``negative thermal expansion'' and phase transitions connected to insertion/de-insertion of alcohols upon temperature variations reported earlier for graphite oxide powders. Therefore, GO membranes are a distinct type of material with unique solvation properties compared to parent graphite oxides even if they are composed of the same graphene oxide flakes.The structure of graphene oxide (GO) membranes was studied in situ in liquid solvents using synchrotron radiation X-ray diffraction in a broad temperature interval. GO membranes are hydrated by water similarly to precursor graphite oxide powders but intercalation of alcohols is strongly hindered, which explains why the GO membranes are permeated by water and not by ethanol. Insertion of ethanol into the membrane structure is limited to only one monolayer in the whole studied temperature range, in contrast to precursor graphite oxide powders, which are intercalated with up to two ethanol monolayers (Brodie) and four ethanol monolayers (Hummers). As a result, GO membranes demonstrate the absence of ``negative thermal expansion'' and phase transitions connected to insertion/de-insertion of alcohols upon temperature variations reported earlier for graphite oxide powders. Therefore, GO membranes are a distinct type of material with unique solvation properties compared to parent graphite oxides even if they are composed of the same graphene oxide flakes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr04631a

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silva, Camila F.N.; Lazarin, Angélica M., E-mail: amlazarin2@uem.br; Sernaglia, Rosana L.

Graphical abstract: Scanning electron microscopy photographs of calcium phosphate (a) and intercalated with p-aminobenzoic acid (b). Highlights: ► Calcium phosphate was intercalated with p-aminobenzoic acid. ► Guest molecule contains nitrogen and oxygen atoms from amine and carboxylic groups. ► These basic centers are potentially useful for cation coordination in ethanol solution. ► Crystal morphology of compounds is lamellar, it agrees with expected structural characteristics. -- Abstract: Crystalline lamellar calcium phosphate retained 4-aminobenzoic acid inside its cavity without leaching. The intense infrared bands in the 1033 and 1010 cm{sup −1} interval confirmed the presence of the phosphonate groups attached to themore » inorganic layer, with sharp and intense peaks in X-ray diffraction patterns, which gave basal distances of 712 and 1578 pm for the original and the intercalated compounds, respectively. Solid-state {sup 31}P nuclear magnetic resonance spectra presented only one peak for the phosphate groups attached to the main inorganic polymeric structure near −2.4 ppm. The adsorption isotherms from ethanol gave the maximum adsorption capacities of 6.44 and 3.34 mmol g{sup −1} for nickel and cobalt, respectively, which stability constant and distribution coefficient followed Co > Ni.« less

Asymmetric supercapacitors based on electrospun carbon nanofiber/sodium-pre-intercalated manganese oxide electrodes with high power and energy densities

NASA Astrophysics Data System (ADS)

Lin, Sheng-Chi; Lu, Yi-Ting; Chien, Yu-An; Wang, Jeng-An; Chen, Po-Yu; Ma, Chen-Chi M.; Hu, Chi-Chang

2018-07-01

The sodium-pre-intercalated δ-MnO2 is in-situ grown on carbon nanofiber via a simple, one-step method for the application of asymmetric supercapacitors. The pre-intercalation of Na ions into the layered structure of δ-MnO2 reduces the crystallinity, beneficial to Na+ diffusion into/out the interlayer structure and pseudocapacitive utilization of MnO2. This NaxMnO2@CNF nanocomposite with desirable pseudo-capacitance from δ-NaxMnO2 and high electric conductivity from CNF network shows a high specific capacitance of 321 F g-1 at 1 A g-1 with ca. 75.2% capacitance retention from 1 to 32 A g-1. An ASC cell consisting of this nanocomposite and activated carbon as the positive and negative electrodes can be reversibly charged and discharged to a cell voltage of 2.0 V in 1 M Na2SO4 and 4 mM NaHCO3 with specific energy and power of 21 Wh kg-1 and 1 kW kg-1, respectively. This ASC also shows excellent cell capacitance retention (7% decay) in the 2 V, 10,000-cycle stability test, revealing superior performance.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Direct growth of 2D nickel hydroxide nanosheets intercalated with polyoxovanadate anions as a binder-free supercapacitor electrode.

PubMed

Gunjakar, Jayavant L; Inamdar, Akbar I; Hou, Bo; Cha, SeungNam; Pawar, S M; Abu Talha, A A; Chavan, Harish S; Kim, Jongmin; Cho, Sangeun; Lee, Seongwoo; Jo, Yongcheol; Kim, Hyungsang; Im, Hyunsik

2018-05-17

A mesoporous nanoplate network of two-dimensional (2D) layered nickel hydroxide Ni(OH)2 intercalated with polyoxovanadate anions (Ni(OH)2-POV) was built using a chemical solution deposition method. This approach will provide high flexibility for controlling the chemical composition and the pore structure of the resulting Ni(OH)2-POV nanohybrids. The layer-by-layer ordered growth of the Ni(OH)2-POV is demonstrated by powder X-ray diffraction and cross-sectional high-resolution transmission electron microscopy. The random growth of the intercalated Ni(OH)2-POV nanohybrids leads to the formation of an interconnected network morphology with a highly porous stacking structure whose porosity is controlled by changing the ratio of Ni(OH)2 and POV. The lateral size and thickness of the Ni(OH)2-POV nanoplates are ∼400 nm and from ∼5 nm to 7 nm, respectively. The obtained thin films are highly active electrochemical capacitor electrodes with a maximum specific capacity of 1440 F g-1 at a current density of 1 A g-1, and they withstand up to 2000 cycles with a capacity retention of 85%. The superior electrochemical performance of the Ni(OH)2-POV nanohybrids is attributed to the expanded mesoporous surface area and the intercalation of the POV anions. The experimental findings highlight the outstanding electrochemical functionality of the 2D Ni(OH)2-POV nanoplate network that will provide a facile route for the synthesis of low-dimensional hybrid nanomaterials for a highly active supercapacitor electrode.

Dynamics of graphite fiber intercalation: In situ resistivity measurements with a four point probe

NASA Technical Reports Server (NTRS)

Jaworske, D. A.

1984-01-01

The dynamics of ferric chloride intercalation of single graphite fibers were studied, in situ, using a four point dc bridge. Measurements before, during and after the intercalation showed that the intercalation occurred within minutes at 200 C. Changes in fiber resistivity after exposure to air suggested hydration of the graphite intercalation compound. Deintercalation of the ferric chloride was initiated at temperatures in excess of 400 C. cycling the intercalant into and out of the graphite fiber gave no improvements in fiber resistivity. The activation energy of the ferric chloride intercalation reaction was found to be 17 + or - 4 kcal/mol 1 consistent with the concept of a preliminary nucleation step in the intercalation reaction.

Cost Structure and Life Cycle Cost (LCC) for Military Systems (structures de couts globaux de possession (LCC) pour systemes militaires)

DTIC Science & Technology

2003-06-01

variables. Dans le plan (p = 2), la méthode de régression linéaire ajuste au nuage de points une droite qui minimise la somme des écarts au carré entre...cohérence de la définition du produit. Par exemple, pour un blindé, il faut valider l ’ « harmonie » du trio masse, puissance du moteur et vitesse maximale. Il...en condition opérationnelle. De façon plus générale, la DGA devrait s’orienter vers l ‘élaboration et l’acquisition de modèle d’estimation de coûts du

Decoupling of epitaxial graphene via gold intercalation probed by dispersive Raman spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pillai, P. B., E-mail: p.pillai@sheffield.ac.uk, E-mail: m.desouza@sheffield.ac.uk; DeSouza, M., E-mail: p.pillai@sheffield.ac.uk, E-mail: m.desouza@sheffield.ac.uk; Narula, R.

Signatures of a superlattice structure composed of a quasi periodic arrangement of atomic gold clusters below an epitaxied graphene (EG) layer are examined using dispersive Raman spectroscopy. The gold-graphene system exhibits a laser excitation energy dependant red shift of the 2D mode as compared to pristine epitaxial graphene. The phonon dispersions in both the systems are mapped using the experimentally observed Raman signatures and a third-nearest neighbour tight binding electronic band structure model. Our results reveal that the observed excitation dependent Raman red shift in gold EG primarily arise from the modifications of the phonon dispersion in gold-graphene and showsmore » that the extent of decoupling of graphene from the underlying SiC substrate can be monitored from the dispersive nature of the Raman 2D modes. The intercalated gold atoms restore the phonon band structure of epitaxial graphene towards free standing graphene.« less

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

NASA Astrophysics Data System (ADS)

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

2013-07-01

Direct reaction of ZnO with 2,4-dichlorophenoxyacetic acid (24D) solutions of different concentrations allows obtaining new organic-inorganic nanohybrid materials formed by intercalation of 24D into interlayers of zinc layered hydroxide (ZLH). XRD patterns show a progressive evolution of the structure as 24D concentration increases. The nanohybrid obtained at higher 24D concentration (24D-ZLH(0.4)) reveals a well ordered layered structure with two different basal spacings at 25.2 Å and 24 Å. The FTIR spectrum showing the vibrations bands of the functional groups of 24D and of the ZLH confirms the intercalation. SEM images are in agreement with the structural evolution observed by XRD and reveal the ribbon morphology of the nanohybrids. The release studies of 24D showed a rapid release of 94% for the first 100 min governed by the pseudo-second order kinetic model.

Between Scylla and Charybdis: Hydrophobic Graphene-Guided Water Diffusion on Hydrophilic Substrates

PubMed Central

Kim, Jin-Soo; Choi, Jin Sik; Lee, Mi Jung; Park, Bae Ho; Bukhvalov, Danil; Son, Young-Woo; Yoon, Duhee; Cheong, Hyeonsik; Yun, Jun-Nyeong; Jung, Yousung; Park, Jeong Young; Salmeron, Miquel

2013-01-01

The structure of water confined in nanometer-sized cavities is important because, at this scale, a large fraction of hydrogen bonds can be perturbed by interaction with the confining walls. Unusual fluidity properties can thus be expected in the narrow pores, leading to new phenomena like the enhanced fluidity reported in carbon nanotubes. Crystalline mica and amorphous silicon dioxide are hydrophilic substrates that strongly adsorb water. Graphene, on the other hand, interacts weakly with water. This presents the question as to what determines the structure and diffusivity of water when intercalated between hydrophilic substrates and hydrophobic graphene. Using atomic force microscopy, we have found that while the hydrophilic substrates determine the structure of water near its surface, graphene guides its diffusion, favouring growth of intercalated water domains along the C-C bond zigzag direction. Molecular dynamics and density functional calculations are provided to help understand the highly anisotropic water stripe patterns observed. PMID:23896759

Electron Transfer Governed Crystal Transformation of Tungsten Trioxide upon Li Ions Intercalation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhiguo; He, Yang; Gu, Meng

2016-09-21

Reversible insertion/extraction of ions into a host lattice constitutes the fundamental operating principle of rechargeable battery and electrochromic materials. It is far more commonly observed that insertion of ions into a host lattice can lead to structural evolution of the host lattice, and for the most cases such a lattice evolution is subtle. However, it has never been clear as what kind of factors to control such a lattice structural evolution. Based on tungsten trioxide (WO3) model crystal, we use in situ transmission electron microscopy (TEM) and first principles calculation to explore the nature of Li ions intercalation induced crystalmore » symmetry evolution of WO3. We discovered that Li insertion into the octahedral cavity of WO3 lattice will lead to a low to high symmetry transition, featuring a sequential monoclinic→tetragonal→cubic phase transition. The first principle calculation reveals that the phase transition is essentially governed by the electron transfer from Li to the WO6 octahedrons, which effectively leads to the weakening the W-O bond and modifying system band structure, resulting in an insulator to metal transition. The observation of the electronic effect on crystal symmetry and conductivity is significant, providing deep insights on the intercalation reactions in secondary rechargeable ion batteries and the approach for tailoring the functionalities of material based on insertion of ions in the lattice.« less

Nanoporous-carbon as a potential host material for reversible Mg ion intercalation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siegal, Michael P.; Yelton, W. Graham; Perdue, Brian R.

Here, we study nanoporous-carbon (NPC) grown via pulsed laser deposition (PLD) as an electrically conductive anode host material for Mg 2+ intercalation. NPC has high surface area, and an open, accessible pore structure tunable via mass density that can improve diffusion. We fabricate 2032 coin cells using NPC coated stainless-steel disk anodes, metallic Mg cathodes, and a Grignard-based electrolyte. NPC mass density is controlled during growth, ranging from 0.06–1.3 g/cm 3. The specific surface area of NPC increases linearly from 1,000 to 1,700 m 2/g as mass density decreases from 1.3 to 0.26 g/cm 3, however, the surface area fallsmore » off dramatically at lower mass densities, implying a lack of mechanical integrity in such nanostructures. These structural characterizations correlate directly with coin cell electrochemical measurements. In particular, cyclic voltammetry (CV) scans for NPC with density ~0.5 g/cm 3 and BET surface area ~1500 m 2/g infer the possibility of reversible Mg-ion intercalation. Higher density NPC yields capacitive behavior, most likely resulting from the smaller interplanar spacings between graphene sheet fragments and tighter domain boundaries; lower density NPC results in asymmetrical CV scans, consistent with the likely structural degradation resulting from mass transport through soft, low-density carbon materials.« less

Nanoporous-carbon as a potential host material for reversible Mg ion intercalation

DOE PAGES

Siegal, Michael P.; Yelton, W. Graham; Perdue, Brian R.; ...

2016-03-25

Here, we study nanoporous-carbon (NPC) grown via pulsed laser deposition (PLD) as an electrically conductive anode host material for Mg 2+ intercalation. NPC has high surface area, and an open, accessible pore structure tunable via mass density that can improve diffusion. We fabricate 2032 coin cells using NPC coated stainless-steel disk anodes, metallic Mg cathodes, and a Grignard-based electrolyte. NPC mass density is controlled during growth, ranging from 0.06–1.3 g/cm 3. The specific surface area of NPC increases linearly from 1,000 to 1,700 m 2/g as mass density decreases from 1.3 to 0.26 g/cm 3, however, the surface area fallsmore » off dramatically at lower mass densities, implying a lack of mechanical integrity in such nanostructures. These structural characterizations correlate directly with coin cell electrochemical measurements. In particular, cyclic voltammetry (CV) scans for NPC with density ~0.5 g/cm 3 and BET surface area ~1500 m 2/g infer the possibility of reversible Mg-ion intercalation. Higher density NPC yields capacitive behavior, most likely resulting from the smaller interplanar spacings between graphene sheet fragments and tighter domain boundaries; lower density NPC results in asymmetrical CV scans, consistent with the likely structural degradation resulting from mass transport through soft, low-density carbon materials.« less

Formation of intercalation compound of kaolinite-glycine via displacing guest water by glycine.

PubMed

Zheng, Wan; Zhou, Jing; Zhang, Zhenqian; Chen, Likun; Zhang, Zhongfei; Li, Yong; Ma, Ning; Du, Piyi

2014-10-15

The kaolinite-glycine intercalation compound was successfully formed by displacing intercalated guest water molecules in kaolinite hydrate as a precursor. The microstructure of the compound was characterized by X-ray diffraction, Fourier Transform Infrared Spectroscopy and Scanning Electron Microscope. Results show that glycine can only be intercalated into hydrated kaolinite to form glycine-kaolinite by utilizing water molecules as a transition phase. The intercalated glycine molecules were squeezed partially into the ditrigonal holes in the silicate layer, resulting in the interlayer distance of kaolinite reaching 1.03nm. The proper intercalation temperature range was between 20°C and 80°C. An intercalation time of 24h or above was necessary to ensure the complete formation of kaolinite-glycine. The highest intercalation degree of about 84% appeared when the system was reacted at the temperature of 80°C for 48h. There were two activation energies for the intercalation of glycine into kaolinite, one being 21kJ/mol within the temperature range of 20-65°C and the other 5.8kJ/mol between 65°C and 80°C. The intercalation degree (N) and intercalation velocity (v) of as a function of intercalation time (t) can be empirically expressed as N=-79.35e(-)(t)(/14.8)+80.1 and v=5.37e(-)(t)(/14.8), respectively. Copyright © 2014 Elsevier Inc. All rights reserved.

Synthesis and electrical characterization of magnetic bilayer graphene intercalate.

PubMed

Kim, Namdong; Kim, Kwang S; Jung, Naeyoung; Brus, Louis; Kim, Philip

2011-02-09

We report synthesis and transport properties of the minimal graphite intercalation compound, a ferric chloride (FeCl(3))(n) island monolayer inside bilayer graphene. Chemical doping by the intercalant is simultaneously probed by micro-Raman spectroscopy and Hall measurements. Quantum oscillations of conductivity originate from microscopic domains of intercalated and unintercalated regions. A slight upturn in resistance related to magnetic transition is observed. Two-dimensional intercalation in bilayer graphene opens new possibilities to engineer two-dimensional properties of intercalates.

Superconductivity in graphite intercalation compounds

DOE PAGES

Smith, Robert P.; Weller, Thomas E.; Howard, Christopher A.; ...

2015-02-26

This study examines the field of superconductivity in the class of materials known as graphite intercalation compounds which has a history dating back to the 1960s. 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 this relates to theoretical studies. The bulk of the evidence strongly supports a BCS superconducting state. However, important questions remain regarding which electronic statesmore » 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.« less

First principles calculations of stability and lithium intercalation potentials of ZnCo2O4

NASA Astrophysics Data System (ADS)

Yu, L. C.; Wu, J.; Liu, H.; Zhang, Y. N.

2015-03-01

Among the metal oxides, which are the most widely investigated alternative anodes for use in lithium ion batteries (LIBs), binary and ternary tin oxides have received special attention due to their high capacity values. ZnCo2O4 is a promising candidate as the anode material for LIB, and one can expect a total capacity corresponding to 7.0 - 8.33 mol of recyclable Li per mole of ZnCo2O4. Here we studied the structural stability, electronic properties, diffusion barrier and lithium intercalation potentials of ZnCo2O4 through density functional calculations. The calculated structural and energetic parameters are comparable with experiments. Our DFT studies provide insights in understanding the mechanism of lithium ion displacement reactions in this ternary metal oxide.

Influence of sodium dodecyl sulfate concentration on the photocatalytic activity and dielectric properties of intercalated sodium dodecyl sulfate into Zn–Cd–Al layered double hydroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmed, Abdullah Ahmed Ali, E-mail: abdullah2803@gmail.com; Talib, Zainal Abidin; Hussein, Mohd Zobir

2015-02-15

Highlights: • Zn–Cd–Al–LDH–DS were synthesized with different SDS concentrations. • Photocatalytic activity of samples was improved by increasing SDS concentration. • Dielectric response of LDH can be described by anomalous low frequency dispersion. • The dc conductivity values were calculated for Zn–Cd–Al–LDH–DS samples. • ESR spectra exhibited the successful intercalation of DS molecule into LDH gallery. - Abstract: Sodium dodecyl sulfate (SDS) has been successfully intercalated into Zn–Cd–Al–LDH precursor with different SDS concentrations (0.2, 0.3, 0.4, 0.5 and 1 mol L{sup −1}) using the coprecipitation method at (Zn{sup 2+} + Cd{sup 2+})/Al{sup 3+} molar ratio of 13 and pH 8.more » The structural, morphological, texture and composition properties of the synthesized (Zn–Cd–Al–LDH–DS) nanostructure were investigated using powder X-ray diffraction (PXRD), scanning electron microscope (SEM), thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR), respectively. The photocatalytic activity of these materials was developed by increasing the concentration of intercalated SDS. The absorbance spectra have been used to detect an anion in the LDH interlayer before and after the intercalation process, which confirmed the presence of the dodecyl sulfate (DS{sup −}) anion into LDH gallery after intercalation. The anomalous low frequency dispersion (ALFD) has been used to describe the dielectric response of Zn–Cd–Al–LDH–DS nanostructure using the second type of universal power law. At low frequency, the polarization effect of electrodes caused the rising in dielectric constant and loss values. An important result of the dielectric measurements is the calculated dc conductivity values, which are new in dielectric spectroscopy of LDH materials. An important result of the electron spin resonance (ESR) spectra exhibited the successful intercalation of DS molecule into LDH gallery. The g-factor value was affected by the SDS concentration which indicated changes to the environment around the DS molecule in LDH interlayer.« less

The 13C nuclear magnetic resonance in graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Resing, H. A.

1985-01-01

The (13)C NMR chemical shifts of graphite intercalation compounds were 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.

C-13 nuclear magnetic resonance in graphite intercalation compounds

NASA Technical Reports Server (NTRS)

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.

CFD Simulations of a Ferry in Head Seas

DTIC Science & Technology

2011-03-01

la durée de vie en fatigue globale du navire. Il est important, pour la conception, l’exploitation et la gestion du cycle de ...vibration de frottement qui exerce une contrainte sur la structure de coque primaire et qui a un effet défavorable sur la durée de vie en fatigue globale du ...laquelle ne peut simuler directement la physique du tossage. Le présent rapport contient les résultats d’une étude faisant

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CO2: Implications for Caprock Integrity

NASA Astrophysics Data System (ADS)

Loring, J. S.; Chen, J.; Thompson, C.; Schaef, T.; Miller, Q. R.; Martin, P. F.; Ilton, E. S.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

2012-12-01

The effectiveness of geologic sequestration as an enterprise for CO2 storage depends partly on the reactivity of supercritical CO2 (scCO2) with caprock minerals. Injection of scCO2 will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Caprock formations have high concentrations of clay minerals, including expandable montmorillonites. Water-bearing scCO2 is highly reactive and capable of hydrating or dehydrating clays, possibly leading to porosity and permeability changes that directly impact caprock performance. Dehydration will cause montmorillonite clay minerals in caprocks to contract, thereby decreasing solid volume and possibly increasing caprock permeability and porosity. On the other hand, water intercalation will cause these clays to expand, thereby increasing solid volume and possibly leading to self-sealing of caprock fractures. Pacific Northwest National Laboratory's Carbon Sequestration Initiative is developing capabilities for studying wet scCO2-mineral reactions in situ. Here, we introduce novel in situ infrared (IR) spectroscopic instrumentation that enables quantitative titrations of reactant minerals with water in scCO2. Results are presented for the infrared spectroscopic titrations of Na-, Ca-, and Mg-saturated Wyoming betonites with water over concentrations ranging from zero to scCO2 saturated. These experiments were carried out at 50°C and 90 bar. Transmission IR spectroscopy was used to measure concentrations of water dissolved in the scCO2 or intercalated into the clays. The titration curves evaluated from the transmission-IR data are compared between the three types of clays to assess the effects of the cation on water partitioning. Single-reflection attenuated total reflection (ATR) IR spectroscopy was used to collect the spectrum of the clays as they hydrate at every total water concentration during the titration. Clay hydration is evidenced by increases in absorbance of the OH stretching and HOH bending modes of the intercalated waters. The ATR-IR data also indicate that CO2 is intercalated in the clay. The asymmetric stretching band of the CO2 molecules that are intercalated in the clay is narrower than that stretching band of bulk scCO2, which indicates that the spectral contribution from rotational fine structure is minimal and the intercalated CO2 is rotationally constrained. A chemometrics analysis of the complete set of ATR-IR spectra spanning the range of total water concentrations covered in the titration finds that there are at least two types of intercalated waters, two types of intercalated CO2 molecules, and the concentrations of these intercalated waters and CO2 molecules are correlated. These quantitative data, when coupled with in situ XRD results that predict interlayer spacing and clay volume, demonstrate that water and CO2 intercalation processes in expandable montmorillonite clays could lead to porosity and permeability changes that directly impact caprock performance.

Treasure Na-ion anode from trash coke by adept electrolyte selection

NASA Astrophysics Data System (ADS)

Cabello, Marta; Chyrka, Taras; Klee, Rafael; Aragón, María J.; Bai, Xue; Lavela, Pedro; Vasylchenko, Gennadiy M.; Alcántara, Ricardo; Tirado, José L.; Ortiz, Gregorio F.

2017-04-01

Converting 'trash' waste residua to active functional materials 'treasure' with high added value is being regarded as a promising way to achieve the sustainable energy demands. Carbonaceous materials cannot insert sodium except when graphite co-intercalates solvents such as diglyme. Here, we show that petroleum coke and shale coke annealed at different temperatures can also insert sodium by reversible intercalation phenomena in a diglyme-based electrolyte. The structural and morphological studies will reveal significant differences justifying their distinct electrochemical behavior. Galvanostatic tests exhibit a flat plateau at about 0.7 V ascribable to the reversible reaction. At the end of the discharge, a Stage-I ternary intercalation compound is detected. Two diglyme molecules are co-intercalated per alkali ion, as evidenced by 1-D Patterson diagrams, FTIR and TGA analyses. The full sodium-ion cell made with P-2500/NaPF6(diglyme)/Na3V2(PO4)3 delivered an initial reversible capacity of 75 mA h g-1 at C rate and an average potential of 2.7 V. Thus, the full cell provides an energy density of 202 W h kg-1. This sodium-ion system can be considered a promising power source that encourages the potential use of low-cost energy storage systems.

Magnetic ordering of nickel hydroxide layers 30 Å apart obtained by intercalating dodecyl sulfate

NASA Astrophysics Data System (ADS)

Seehra, M. S.; Singh, V.

2013-09-01

The nature of magnetic ordering in quasi-2D layered hydroxide of Ni (LH-Ni-DS) with hexagonal structure and synthesized by intercalating dodecyl sulfate (DS) ligand, (C12H25OSO3)-, between the layers using a hydrothermal technique is investigated. The observation of (00l) peaks up to l = 8 in x-ray diffraction on the sample yields an interlayer spacing c ≃ 30.5 Å and a crystallite size ≃ 16 nm. Assignment of the lines observed in the FTIR spectra to the various groups of the DS ligand confirms the intercalation. From the analysis of detailed investigations of the temperature dependence of the magnetization M at different magnetic fields, ac susceptibilities at frequencies from 0.1 to 1 kHz, and electron magnetic resonance spectra at 9.28 GHz, it is concluded that LH-Ni-DS orders ferromagnetically at TC ≃ 23 K. This TC is about 45% higher than TC ≃ 16 K reported for LH-Ni-Ac with c ≃ 8.6 Å obtained by intercalating an acetate ligand between the layers. The roles of the interlayer dipolar interaction, magnetic anisotropy and exchange interactions in determining TC in LH-Ni-L systems for several ligands L yielding different c-axes are discussed.

XRD, TEM, and thermal analysis of Arizona Ca-montmorillonites modified with didodecyldimethylammonium bromide.

PubMed

Sun, Zhiming; Park, Yuri; Zheng, Shuilin; Ayoko, Godwin A; Frost, Ray L

2013-10-15

An Arizona SAz-2 calcium montmorillonite was modified by a typical dialkyl cationic surfactant (didodecyldimethylammonium bromide, abbreviated to DDDMA) through direct ion exchange. The obtained organoclays were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), high-resolution thermogravimetric analysis (HR-TG), and infrared emission spectroscopy (IES). The intercalation of surfactants greatly increased the basal spacing of the interlayers and the conformation arrangement of the loaded surfactant were assessed based on the XRD and TEM measurements. This work shows that the dialkyl surfactant can be directly intercalated into the montmorillonite without first undergoing Na(+) exchange. Moreover, the thermal stability of organoclays and the different arrangements of the surfactant molecules intercalated in the SAz-2 Ca-montmorillonite were determined by a combination of TG and IES techniques. The detailed conformational ordering of different intercalated surfactants under different conditions was also studied. The surfactant molecule DDDMA has proved to be thermally stable even at 400°C which indicates that the prepared organoclay is stable to significantly high temperatures. This study offers new insights into the structure and thermal stabilities of SAz-2 Ca-montmorillonite modified with DDDMA. The experimental results also confirm the potential applications of organic SAz-2 Ca-montmorillonites as adsorbents and polymer-clay nanocomposites. Copyright © 2013 Elsevier Inc. All rights reserved.

C-1311 (Symadex), a potential anti-cancer drug, intercalates into DNA between A and G moieties. NMR-derived and MD-refined stereostructure of the d(GAGGCCTC)2:C-1311 complex

NASA Astrophysics Data System (ADS)

Laskowski, Tomasz; Borzyszkowska, Julia; Grynda, Jakub; Mazerski, Jan

2017-08-01

Imidazoacridinone C-1311 (Symadex®) is an antitumor agent which has been recommended for Phase II clinical trials a few years ago. Previously, it was shown experimentally that during the initial stage of its action C-1311 forms stable intercalation complexes with DNA duplexes. Herein, a NMR-derived stereostructure of d(GAGGCCTC)2:C-1311 complex was reported. The ligand was found locating itself between A and G moieties, forming symmetrical DNA:drug 1:2 mol/mol complex. Intercalation site was located upon the DNA-ligand proton/proton dipolar couplings observed in the NOESY spectrum and the performed MD simulations. NMR-derived stereostructure was hence refined by restrained MD using distance restraints obtained from the NOESY data and the result was compared with MD-derived structure of the proposed complex, obtained from the calculations performed with distance restraints applied only for hydrogen bonds in the terminal GC base pairs. The results of both simulations were coherent. Basing on the observed C-1311's intercalation sites and on our previous results concerning the d(CGATCG)2:C-1311 complex, we stated that AG/GA sequences are the preferred binding sites of imidazoacridinone C-1311.

First-principles characterization of potassium intercalation in the hexagonal 2H-MoS2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersen, Amity; Kathmann, Shawn M.; Lilga, Michael A.

2012-01-12

Periodic density functional theory calculations were performed to study the structural and electronic properties of potassium intercalated into hexagonal MoS{sub 2} (2H-MoS{sub 2}). Metallic potassium (K) atoms are incrementally loaded in the hexagonal sites of the interstitial spaces between MoS2 sheets of the 2H-MoS{sub 2} bulk structure generating 2H-KxMoS2 (0.125 {<=} x {<=} 1.0) structures. To accommodate the potassium atoms, the interstitial spacing c parameter in the 2H-MoS{sub 2} bulk expands from 12.816 {angstrom} in 2H-MoS{sub 2} to 16.086 {angstrom} in 2H-K{sub 0.125}MoS{sub 2}. The second lowest potassium loading concentration (K{sub 0.25}MoS{sub 2}) results in the largest interstitial spacing expansionmore » (to c = 16.726 {angstrom}). Our calculations show that there is a small gradual contraction of the interstitial spacing as the potassium loading increases with c = 14.839 {angstrom} for KMoS{sub 2}. This interstitial contraction is correlated with an in-plane expansion of the MoS{sub 2} sheets, which is in good agreement with experimental X-ray diffraction (XRD) measurements. The electronic analysis shows that potassium readily donates its 4s electron to the conduction band of the 2H-K{sub x}MoS{sub 2}, and is largely ionic in character. As a result of the electron donation, the 2H-K{sub x}MoS{sub 2} system changes from a semiconductor to a more metallic system with increasing potassium intercalation. For loadings 0.25 {<=} x {<=} 0.625, triangular Mo-Mo-Mo moieties are prominent and tend to form rhombitrihexagonal motifs. Intercalation of H{sub 2}O molecules that solvate the K atoms is likely to occur in catalytic conditions. The inclusion of two H{sub 2}O molecules per K atom in the K{sub 0.25}MoS{sub 2} structure shows good agreement with XRD measurements.« less

Noble-metal intercalation process leading to a protected adatom in a graphene hollow site

NASA Astrophysics Data System (ADS)

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].

A new solution chemical method to make low dimensional thermoelectric materials

NASA Astrophysics Data System (ADS)

Ding, Zhongfen

2001-11-01

Bismuth telluride and its alloys are currently the best thermoelectric materials known at room temperature and are therefore used for portable solid-state refrigeration. If the thermal electric figure of merit ZT could be improved by a factor of about 3, quiet and rugged solid-state devices could eventually replace conventional compressor based cooling systems. In order to test a theory that improved one-dimensional or two-dimensional materials could enhance ZT due to lower thermal conductivity, we are developing solution processing methods to make low dimensional materials. Bismuth telluride and its p-type and n-type alloys have layered structures consisting of 5 atom thick Te-Bi-Te-Bi-Te sheets, each sheet about 10 A thick. Lithium ions are intercalated into the layered materials using liquid ammonia. The lithium-intercalated materials are then exfoliated in water to form colloidal suspensions with narrow particle size distributions and are stable for more than 24 hours. The layers are then deposited on substrates, which after annealing at low temperatures, form highly c-axis oriented thin films. The exfoliated layers can potentially be restacked with other ions or layered materials in between the sheets to form novel structures. The restacked layers when treated with nitric acid and sonication form high yield nanorod structured materials. This new intercalation and exfoliation followed by sonication method could potentially be used for many other layered materials to make nanorod structured materials. The low dimensional materials are characterized by powder X-ray diffraction, atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), inductively coupled plasma (ICP) and dynamic light scattering.

Effect of type and content of modified montmorillonite on the structure and properties of bio-nanocomposite films based on soy protein isolate and montmorillonite.

PubMed

Kumar, P; Sandeep, K P; Alavi, S; Truong, V D; Gorga, R E

2010-06-01

The nonbiodegradable and nonrenewable nature of plastic packaging has led to a renewed interest in packaging materials based on bio-nanocomposites (biopolymer matrix reinforced with nanoparticles such as layered silicates). Bio-nanocomposite films based on soy protein isolate (SPI) and modified montmorillonite (MMT) were prepared using melt extrusion. The effect of different type (Cloisite 20A and Cloisite 30B) and content (0% to 15%) of modified MMT on the structure (degree of intercalation and exfoliation) and properties (color, mechanical, dynamic mechanical, thermal stability, and water vapor permeability) of SPI-MMT bio-nanocomposite films were investigated. Extrusion of SPI and modified MMTs resulted in bio-nanocomposites with exfoliated structures at lower MMT content (5%). At higher MMT content (15%), the structure of bio-nanocomposites ranged from intercalated for Cloisite 20A to disordered intercalated for Cloisite 30B. At an MMT content of 5%, bio-nanocomposite films based on modified MMTs (Cloisite 20A and Cloisite 30B) had better mechanical (tensile strength and percent elongation at break), dynamic mechanical (glass transition temperature and storage modulus), and water barrier properties as compared to those based on natural MMT (Cloisite Na(+)). Bio-nanocomposite films based on 10% Cloisite 30B had mechanical properties comparable to those of some of the plastics that are currently used in food packaging applications. However, much higher WVP values of these films as compared to those of existing plastics might limit the application of these films to packaging of high moisture foods such as fresh fruits and vegetables.

Selective sodium intercalation into sodium nickel-manganese sulfate for dual Na-Li-ion batteries.

PubMed

Marinova, Delyana M; Kukeva, Rosica R; Zhecheva, Ekaterina N; Stoyanova, Radostina K

2018-05-09

Double sodium transition metal sulfates combine in themselves unique intercalation properties with eco-compatible compositions - a specific feature that makes them attractive electrode materials for lithium and sodium ion batteries. Herein, we examine the intercalation properties of novel double sodium nickel-manganese sulfate, Na2Ni1/2Mn1/2(SO4)2, having a large monoclinic unit cell, through electrochemical and ex situ diffraction and spectroscopic methods. The sulfate salt Na2Ni1/2Mn1/2(SO4)2 is prepared by thermal dehydration of the corresponding hydrate salt Na2Ni1/2Mn1/2(SO4)2·4H2O having a blödite structure. The intercalation reactions on Na2Ni1-xMnx(SO4)2 are studied in two model cells: half-ion cell versus Li metal anode and full-ion cell versus Li4Ti5O12 anode by using lithium (LiPF6 dissolved in EC/DMC) and sodium electrolytes (NaPF6 dissolved in EC:DEC). Based on ex situ XRD and TEM analysis, it is found that sodium intercalation into Na2Ni1/2Mn1/2(SO4)2 takes place via phase separation into the Ni-rich monoclinic phase and Mn-rich alluaudite phase. The redox reactions involving participation of manganese and titanium ions are monitored by ex situ EPR spectroscopy. It has been demonstrated that manganese ions from the sulfate salt are participating in the electrochemical reaction, while the nickel ions remain intact. As a result, a reversible capacity of about 65 mA h g-1 is reached. The selective intercalation properties determine sodium nickel-manganese sulfate as a new electrode material for hybrid lithium-sodium ion batteries that is thought to combine the advantages of individual lithium and sodium batteries.

Composition driven monolayer to bilayer transformation in a surfactant intercalated Mg-Al layered double hydroxide.

PubMed

Naik, Vikrant V; Chalasani, Rajesh; Vasudevan, S

2011-03-15

The structure and organization of dodecyl sulfate (DDS) surfactant chains intercalated in an Mg-Al layered double hydroxide (LDH), Mg(1-x)Alx(OH)2, with differing Al/Mg ratios has been investigated. The Mg-Al LDHs can be prepared over a range of compositions with x varying from 0.167 to 0.37 and therefore provides a simple system to study how the organization of the alkyl chains of the intercalated DDS anions change with packing density; the Al/Mg ratio or x providing a convenient handle to do so. Powder X-ray diffraction measurements showed that at high packing densities (x ≥ 0.3) the alkyl chains of the intercalated dodecyl sulfate ions are anchored on opposing LDH sheets and arranged as bilayers with an interlayer spacing of ∼27 Å. At lower packing densities (x < 0.2) the surfactant chains form a monolayer with the alkyl chains oriented flat in the galleries with an interlayer spacing of ∼8 Å. For the in between compositions, 0.2 ≤ x < 0.3, the material is biphasic. MD simulations were performed to understand how the anchoring density of the intercalated surfactant chains in the Mg-Al LDH-DDS affects the organization of the chains and the interlayer spacing. The simulations are able to reproduce the composition driven monolayer to bilayer transformation in the arrangement of the intercalated surfactant chains and in addition provide insights into the factors that decide the arrangement of the surfactant chains in the two situations. In the bilayer arrangement, it is the dispersive van der Waals interactions between chains in opposing layers of the anchored bilayer that is responsible for the cohesive energy of the solid whereas at lower packing densities, where a monolayer arrangement is favored, Coulomb interactions between the positively charged Mg-Al LDH sheets and the negatively charged headgroup of the DDS anion dominate.

High-Temperature Intercalated Graphite Fiber Conductors Fabricated

NASA Technical Reports Server (NTRS)

Gaier, James R.

2002-01-01

Composites of intercalated graphite fibers show promise to significantly reduce the weight of electromagnetic interference shielding in spacecraft and aircraft. Bromine intercalated pitch-based fibers have been among the most heavily studied systems because of their attractive electrical and thermal conductivities and their stability over a wide range of environmental conditions. Previous studies found that the resistivity of bromineintercalated graphite fibers began to increase when the fibers were exposed to temperatures in excess of about 200 C in air for long periods of time. If the temperature was as high as 450 C, the resistivity increased dramatically within a few hours. It remained unclear, however, whether the increase was due to deintercalation of the bromine or to air oxidation of the fibers. Studies were initially directed toward determining the temperature at which bromine would deintercalate from the fibers, and perhaps become a hazard to both personnel and equipment. So the mass of bromine-intercalated graphite fibers was carefully monitored as it was heated in an inert atmosphere, since the fibers are known to oxidize at a lower temperature than they deintercalate. What was found was that the fibers, which are about 18-wt% bromine, did not lose any appreciable mass even at temperatures approaching 1000 C. X-ray diffraction studies showed that there were also no changes in the overall structure of the compound. Resistivity measurements indicated that there is some slight degradation in the electronic structure, in that the resistivity increased by a few percent. Overall, the results show that these materials may be suitable for applications at temperatures at least this high, provided oxygen is excluded. This may enable their use in carbon-ceramic, and perhaps even carbon-carbon composites.

Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations

DOE PAGES

Liu, Miao; Rong, Ziqin; Malik, Rahul; ...

2014-12-16

In this study, batteries that shuttle multivalent ions such as Mg 2+ and Ca 2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multivalent cations is considered a major challenge for enabling such multivalent battery technology. In this paper, we use recent advances in high-throughput first-principles calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cations. We estimate the insertion voltage, capacity,more » thermodynamic stability of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn 2O 4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; the voltages of Ca spinels are ~0.2 V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ~1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalent cation species. The activation barrier for the Al³⁺ ion migration in the Mn₂O₄ spinel is very high (~1400 meV for Al 3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely. Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties.« less

Co-intercalation of Mg(2+) and Na(+) in Na(0.69)Fe2(CN)6 as a High-Voltage Cathode for Magnesium Batteries.

PubMed

Kim, Dong-Min; Kim, Youngjin; Arumugam, Durairaj; Woo, Sang Won; Jo, Yong Nam; Park, Min-Sik; Kim, Young-Jun; Choi, Nam-Soon; Lee, Kyu Tae

2016-04-06

Thanks to the advantages of low cost and good safety, magnesium metal batteries get the limelight as substituent for lithium ion batteries. However, the energy density of state-of-the-art magnesium batteries is not high enough because of their low operating potential; thus, it is necessary to improve the energy density by developing new high-voltage cathode materials. In this study, nanosized Berlin green Fe2(CN)6 and Prussian blue Na(0.69)Fe2(CN)6 are compared as high-voltage cathode materials for magnesium batteries. Interestingly, while Mg(2+) ions cannot be intercalated in Fe2(CN)6, Na(0.69)Fe2(CN)6 shows reversible intercalation and deintercalation of Mg(2+) ions, although they have the same crystal structure except for the presence of Na(+) ions. This phenomenon is attributed to the fact that Mg(2+) ions are more stable in Na(+)-containing Na(0.69)Fe2(CN)6 than in Na(+)-free Fe2(CN)6, indicating Na(+) ions in Na(0.69)Fe2(CN)6 plays a crucial role in stabilizing Mg(2+) ions. Na(0.69)Fe2(CN)6 delivers reversible capacity of approximately 70 mA h g(-1) at 3.0 V vs Mg/Mg(2+) and shows stable cycle performance over 35 cycles. Therefore, Prussian blue analogues are promising structures for high-voltage cathode materials in Mg batteries. Furthermore, this co-intercalation effect suggests new avenues for the development of cathode materials in hybrid magnesium batteries that use both Mg(2+) and Na(+) ions as charge carriers.

Excitation and characterization of image potential state electrons on quasi-free-standing graphene

NASA Astrophysics Data System (ADS)

Lin, Yi; Li, Yunzhe; Sadowski, Jerzy T.; Jin, Wencan; Dadap, Jerry I.; Hybertsen, Mark S.; Osgood, Richard M.

2018-04-01

We investigate the band structure of image potential states in quasi-free-standing graphene (QFG) monolayer islands using angle-resolved two-photon-photoemission spectroscopy. Direct probing by low-energy electron diffraction shows that QFG is formed following oxygen intercalation into the graphene-Ir(111) interface. Despite the apparent decoupling of the monolayer graphene from the Ir substrate, we find that the binding energy of the n =1 image potential state on these QFG islands increases by 0.17 eV, as compared to the original Gr/Ir(111) interface. We use calculations based on density-functional theory to construct an empirical, one-dimensional potential that quantitatively reproduces the image potential state binding energy and links the changes in the interface structure to the shift in energy. Specifically, two factors contribute comparably to this energy shift: a deeper potential well arising from the presence of intercalated oxygen adatoms and a wider potential well associated with the increase in the graphene-Ir distance. While image potential states have not been observed previously on QFG by photoemission, our paper now demonstrates that they may be strongly excited in a well-defined QFG system produced by oxygen intercalation. This opens an opportunity for studying the surface electron dynamics in QFG systems, beyond those found in typical nonintercalated graphene-on-substrate systems.

Electron Beam Irradiated Intercalated CNT Yarns For Aerospace Applications

NASA Technical Reports Server (NTRS)

Waters, Deborah L.; Gaier, James R.; Williams, Tiffany S.; Lopez Calero, Johnny E.; Ramirez, Christopher; Meador, Michael A.

2015-01-01

Multi-walled CNT yarns have been experimentally and commercially created to yield lightweight, high conductivity fibers with good tensile properties for application as electrical wiring and multifunctional tendons. Multifunctional tendons are needed as the cable structures in tensegrity robots for use in planetary exploration. These lightweight robust tendons can provide mechanical strength for movement of the robot in addition to power distribution and data transmission. In aerospace vehicles, such as Orion, electrical wiring and harnessing mass can approach half of the avionics mass. Use of CNT yarns as electrical power and data cables could reduce mass of the wiring by thirty to seventy percent. These fibers have been intercalated with mixed halogens to increase their specific electrical conductivity to that near copper. This conductivity, combined with the superior strength and fatigue resistance makes it an attractive alternative to copper for wiring and multifunctional tendon applications. Electron beam irradiation has been shown to increase mechanical strength in pristine CNT fibers through increased cross-linking. Both pristine and intercalated CNT yarns have been irradiated using a 5-megavolt electron beam for various durations and the conductivities and tensile properties will be discussed. Structural information obtained using a field emission scanning electron microscope, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy will correlate microstructural details with bulk properties.

Effects of TiO2 crystal structure on the luminescence quenching of [Ru(bpy)2(dppz)]2 +-intercalated into DNA

NASA Astrophysics Data System (ADS)

Chen, Linlin; Wang, Yi; Huang, Minggao; Li, Xiaodan; Zhu, Licai; Li, Hong

2017-06-01

The intercalation of [Ru(bpy)2(dppz)]2 + labeled as Ru(II) (bpy = 2,2‧-bipyridine and dppz = dipyrido[3,2,-a:2‧,3‧-c]phenazine) into herring sperm DNA leads to the formation of emissive Ru(II)-DNA dyads, which can be quenched by TiO2 nanoparticles (NPs) and sol-gel silica matrices at heterogeneous interfaces. The calcinations temperature exhibits a remarkable influence on the luminescence quenching of the Ru(II)-DNA dyads by TiO2 NPs. With increasing calcinations temperature in the range from 200 to 850 °C, the anatase-to-rutile TiO2 crystal structure transformation increases the average particle size and hydrodynamic diameter of TiO2 and DNA@TiO2. The anatase TiO2 has the stronger ability to unbind the Ru(II)-DNA dyads than the rutile TiO2 at room temperature. The TiO2 NPs and sol-gel silica matrices can quench the luminescence of the Ru(II) complex intercalated into DNA by selectively capturing the negatively DNA and positively charged Ru(II) complex to unbind the dyads, respectively. This present results provide new insights into the luminescence quenching and competitive binding of dye-labeled DNA dyads by inorganic NPs.

Modeling intercalated PAH metabolites: Explanation for the stereochemical and shape selectivity of B-DNA for bay-region carcinogens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szentpaly, L.V.; Shamovsky, I.L.

1996-12-31

The equilibrium structures of 22 intercalation complexes of different metabolites of polycyclic aromatic hydrocarbons (PAH) with the dG{sub 2}{lg_bullet}dC{sub 2} dinucleotide are obtained by AMBER and FLEX molecular modeling. The triol carbocations of highly potent carcinogens are stereochemically compatible with the dinucleotide and B-DNA. Their intercalation complexes are found (1) to be stabilized by two hydrogen bonds between DH groups of the triol cation and the N(3) atoms of the adjacent guanine residues, (2) to be {open_quotes}preorganized{close_quotes} for covalent bonding to the N(2) amino group of quanine, (3) to display only minor conformational changes with respect to the uncomplexed dinucleotidemore » in B-DNA. A new explanation for the stereochemical and shape selectivity in the initiation of cancer by PAHa is presented. The molecular mechanics study is sugmented by HF/6-31G{sup I} calculations on the conformations of phenanthrene triol carbocation.« less

Piezo-Electrochemical Energy Harvesting with Lithium-Intercalating Carbon Fibers.

PubMed

Jacques, Eric; Lindbergh, Göran; Zenkert, Dan; Leijonmarck, Simon; Kjell, Maria Hellqvist

2015-07-01

The mechanical and electrochemical properties are coupled through a piezo-electrochemical effect in Li-intercalated carbon fibers. It is demonstrated that this piezo-electrochemical effect makes it possible to harvest electrical energy from mechanical work. Continuous polyacrylonitrile-based carbon fibers that can work both as electrodes for Li-ion batteries and structural reinforcement for composites materials are used in this study. Applying a tensile force to carbon fiber bundles used as Li-intercalating electrodes results in a response of the electrode potential of a few millivolts which allows, at low current densities, lithiation at higher electrode potential than delithiation. More electrical energy is thereby released from the cell at discharge than provided at charge, harvesting energy from the mechanical work of the applied force. The measured harvested specific electrical power is in the order of 1 μW/g for current densities in the order of 1 mA/g, but this has a potential of being increased significantly.

Sub-Surface and Bulk Creep Behaviour of Polyurethane/Clay Nanocomposites.

PubMed

Jin, J; Yusoh, K; Zhang, H X; Song, M

2016-03-01

A series of exfoliated and intercalated polyurethane organoclay nanocomposites were prepared by in situ polymerization of polyol/organoclay mixture, chain extender and diisocyanate. The creep behaviour of subsurface and bulk of the polyurethane coatings was investigated by nanoindentation technique and uniaxial conventional creep testing method, respectively. The results showed that the creep resistance of the nanocomposites was significantly improved by incorporation of organoclay. The enhancement of creep resistance was dependent on clay content as well as organoclay structure (exfoliation or intercalation) in the polymer matrix. With 1 wt% organoclay, the creep resistance increased by about 50% for the intercalated organoclay and 6% for the exfoliated organoclay systems, respectively, compared to the pristine polyurethane. Viscoelastic model was employed to investigate the effect of organoclay loadings on the creep performance of the polyurethane. Results showed the model was in good agreement with the experimental data. Incorporation of clay leads to an increase in elastic deformation especially in exfoliated polyurethane nanocomposites and induces a higher initial displacement at the early stage of creep.

Reversible superconductor-insulator transition in LiTi2O4 induced by Li-ion electrochemical reaction

PubMed Central

Yoshimatsu, K.; Niwa, M.; Mashiko, H.; Oshima, T.; Ohtomo, A.

2015-01-01

Transition metal oxides display various electronic and magnetic phases such as high-temperature superconductivity. Controlling such exotic properties by applying an external field is one of the biggest continuous challenges in condensed matter physics. Here, we demonstrate clear superconductor-insulator transition of LiTi2O4 films induced by Li-ion electrochemical reaction. A compact electrochemical cell of pseudo-Li-ion battery structure is formed with a superconducting LiTi2O4 film as an anode. Li content in the film is controlled by applying a constant redox voltage. An insulating state is achieved by Li-ion intercalation to the superconducting film by applying reduction potential. In contrast, the superconducting state is reproduced by applying oxidation potential to the Li-ion intercalated film. Moreover, superconducting transition temperature is also recovered after a number of cycles of Li-ion electrochemical reactions. This complete reversible transition originates in difference in potentials required for deintercalation of initially contained and electrochemically intercalated Li+ ions. PMID:26541508

Reversible superconductor-insulator transition in LiTi2O4 induced by Li-ion electrochemical reaction.

PubMed

Yoshimatsu, K; Niwa, M; Mashiko, H; Oshima, T; Ohtomo, A

2015-11-06

Transition metal oxides display various electronic and magnetic phases such as high-temperature superconductivity. Controlling such exotic properties by applying an external field is one of the biggest continuous challenges in condensed matter physics. Here, we demonstrate clear superconductor-insulator transition of LiTi2O4 films induced by Li-ion electrochemical reaction. A compact electrochemical cell of pseudo-Li-ion battery structure is formed with a superconducting LiTi2O4 film as an anode. Li content in the film is controlled by applying a constant redox voltage. An insulating state is achieved by Li-ion intercalation to the superconducting film by applying reduction potential. In contrast, the superconducting state is reproduced by applying oxidation potential to the Li-ion intercalated film. Moreover, superconducting transition temperature is also recovered after a number of cycles of Li-ion electrochemical reactions. This complete reversible transition originates in difference in potentials required for deintercalation of initially contained and electrochemically intercalated Li(+) ions.

Synthesis of ktenasite, a double hydroxide of zinc and copper, and its intercalation reaction

NASA Astrophysics Data System (ADS)

Xue, Mei; Chitrakar, Ramesh; Sakane, Kohji; Ooi, Kenta; Kobayashi, Shoichi; Ohnishi, Masayuki; Doi, Akira

2004-04-01

Ktenasite was synthesized by the simple method of mixing ZnO powder with CuSO 4 solution at room temperature. The X-ray diffraction pattern of synthesized ktenasite was very similar to that of mineral ktenasite. The lattice parameters were determined as a=0.559, b=0.616, c=2.374 nm and β=95.63°, which agreed comparatively well with those for mineral ktenasite. The synthesized ktenasite consisted of thin rectangular particles ranging in size from 2 to 4 μm in length. TEM observation suggested the formation of a super lattice structure in the a-axis direction and significant crystal growth in the b-axis direction. The intercalation reaction of sodium dodecyl sulfate (NaDS) with ktenasite showed that the intercalation took place accompanied by the expansion of basal spacing from 1.17 to 2.70 nm. The reaction progressed by the SO 42-/DS - anion exchange mechanism with the dissolution of interlayer [Zn(H 2O) 6]SO 4 salt.

A method to remove intercalates from bromine and iodine intercalated carbon fibers

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1993-01-01

Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers which were intercalated with 18 percent bromine by weight, 1 hr of fluorine exposure results in a large weight increase, but causes only a small decrease in thermal stability. More than l hr of fluorine exposure time results in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena do not occur if the fluorine exposure is at 250 C. These observations suggest the mechanism that at room temperature, fluorine is absorbed quickly by the intercalated fibers and intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. Under an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for two weeks, the brominated fibers lost about 45 percent of their bromine, and their resistivity increased from 64 omega-cm to a range of 95 to 170 micro omega-cm. This is still much lower than the 300 micro omega-cm value for pristine P-100. For practical purposes, in order to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature, or to any intercalate at a temperature where, upon direct contact to graphite, an intercalation compound can easily be formed.

Room-Temperature Fluorine-Induced Decrease in the Stability of Bromine and Iodine Intercalated Carbon Fibers

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1995-01-01

Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers, which were intercalated with 18 wt percent bromine, 1 hour of fluorine exposure resulted in a large weight increase but caused only a small decrease in thermal stability. An additional 89 hours of fluorine exposure time resulted in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena of weight increase and stability decrease do not occur if the intercalated fibers are exposed to 250 C fluorine. These observations suggest that, at room temperature, fluorine is absorbed quickly by the intercalated fibers and is intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. In an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for 2 weeks, the brominated fibers lost about 45% of their bromine, and their resistivity increased from 64 mu(Omega)-cm to a range of 95-170 mu(Omega)-cm. This is still much lower than the value of 300 mu(Omega)-cm for pristine P-100. For practical purposes, to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature or to any intercalate at a temperature where, upon direct contact with graphite, an intercalation compound can easily be formed.

Is it intelligent to intercalate? A two centre cross-sectional study exploring the value of intercalated degrees, and the possible effects of the recent tuition fee rise in England.

PubMed

Stubbs, Timothy Alan; Lightman, Elewys G; Mathieson, Peter

2013-01-24

To explore the value of intercalated degrees, including student perceptions and academic sequelae. To gauge the likely effect of the recent tuition fee rise and to identify any differences in intercalated degrees between Bristol and Sheffield universities. Cross-sectional study using questionnaires. Bristol and Sheffield Medical Schools, UK. 1484 medical students in their clinical years were e-mailed the questionnaire. 578 students responded: 291 from Bristol and 287 from Sheffield (n=578; mean age=22.41; SD 1.944; 38.9% male; 61.1% female). The response rate from previous intercalators was 52.5% from Bristol and 58.7% from Sheffield, while for non-intercalators it was 27.7% and 34.6%, respectively. (1) Student preconceptions, opinions, results and academic sequelae from intercalated degrees at both centres. (2) Students' attitudes concerning the effect of the increase in tuition fees. Those with clinical academic supervisors gained significantly more posters (p=0.0002) and publications (p<0.0001), and also showed a trend to gain more first class honours (p=0.055). Students at Sheffield had a significantly greater proportion of clinical academic supervisors than students at Bristol (p<0.0001). 89.2% said that an intercalated degree was the right decision for them; however, only 27.4% stated they would have intercalated if fees had been £9000 per annum. Students clearly value intercalated degrees, feel they gained a substantial advantage over their peers as well as skills helpful for their future careers. The rise in tuition fees is likely to reduce the number of medical students opting to undertake an intercalated degree, and could result in a further reduction in numbers following an academic path. Sheffield University have more intercalating students supervised by clinical academics. Clinical academics appear more effective as supervisors for medical students undertaking an intercalated degree in terms of results and additional academic sequelae.

Layered Compounds and Intercalation Chemistry: An Example of Chemistry and Diffusion in Solids.

ERIC Educational Resources Information Center

Whittingham, M. Stanley; Chianelli, Russell R.

1980-01-01

Considers a few areas of oxide/sulfide and intercalation-type chemistry. Discusses synthesis of the disulfides of the metals of group IVB, VB, and VIB; the intercalation reaction between lithium and titanium disulfide; other intercalates; and sulfide catalysts. (CS)

Resolving DNA-ligand intercalation in the entropic stretching regime

NASA Astrophysics Data System (ADS)

Almaqwashi, Ali A.

Single molecule studies of DNA intercalation are typically conducted by applying stretching forces to obtain force-dependent DNA elongation measurements. The zero-force properties of DNA intercalation are determined by equilibrium and kinetic force-analysis. However, the applied stretching forces that are above the entropic regime (>5 pN) prevent DNA-DNA contact which may eliminate competitive DNA-ligand interactions. In particular, it is noted that cationic mono-intercalators investigated by single molecule force spectroscopy are mostly found to intercalate DNA with single rate, while bulk studies reported additional slower rates. Here, a proposed framework quantifies DNA intercalation by cationic ligands in competition with relatively rapid kinetic DNA-ligand aggregation. At a constant applied force in the entropic stretching regime, the analysis illustrates that DNA intercalation would be measurably optimized only within a narrow range of low ligand concentrations. As DNA intercalators are considered for potential DNA-targeted therapeutics, this analysis provides insights in tuning ligand concertation to maximize therapeutics efficiency.

Solution structure of a DNA complex with the fluorescent bis-intercalator TOTO determined by NMR spectroscopy.

PubMed

Spielmann, H P; Wemmer, D E; Jacobsen, J P

1995-07-11

We have used two-dimensional 1H NMR spectroscopy to determine the solution structure of the DNA oligonucleotide d(5'-CGCTAGCG-3')2 complexed with the bis-intercalating dye 1,1'-(4,4,8,8-tetramethyl-4,8-diazaundecamethylene)bis[4-(3-methyl -2,3- dihydrobenzo-1,3-thiazolyl-2-methylidene)qui nolinium] tetraiodide (TOTO). The determination of the structure was based on total relaxation matrix analysis of the NOESY cross-peak intensities using the program MARDIGRAS. Improved procedures to consider the experimental "noise" in NOESY spectra during these calculations have been employed. The NOE-derived distance restraints were applied in restrained molecular dynamics calculations. Twenty final structures each were generated for the TOTO complex from both A-form and B-form dsDNA starting structures. The root-mean-square (rms) deviation of the coordinates for the 40 structures of the complex was 1.45 A. The local DNA structure is distorted in the complex. The helix is unwound by 60 degrees and has an overall helical repeat of 12 base pairs, caused by bis-intercalation of TOTO. The poly(propylenamine) linker chain is located in the minor groove of dsDNA. Calculations indicate that the benzothiazole ring system is twisted relative to the quinoline in the uncomplexed TOTO molecule. The site selectivity of TOTO for the CTAG-CTAG site is explained by its ability to adapt to the base pair propeller twist of dsDNA to optimize stacking and the hydrophobic interaction between the thymidine methyl group and the benzothiazole ring. There is a 3000-fold fluorescence enhancement upon binding of TOTO to dsDNA. Rotation about the cyanine methine bonds is possible in free TOTO, allowing relaxation nonradiatively. When bound to dsDNA, the benzothiazole ring and the quinolinium ring are clamped by the nucleobases preventing this rotation, and the chromophore loses excitation energy by fluorescence instead.

Intercalated Nanocomposites Based on High-Temperature Superconducting Ceramics and Their Properties

PubMed Central

Tonoyan, Anahit; Schiсk, Christoph; Davtyan, Sevan

2009-01-01

High temperature superconducting (SC) nanocomposites based on SC ceramics and various polymeric binders were prepared. Regardless of the size of the ceramics’ grains, the increase of their amount leads to an increase of resistance to rupture and modulus and a decrease in limiting deformation, whereas an increase in the average ceramic grain size worsens resistance properties. The SC, thermo-chemical, mechanical and dynamic-mechanical properties of the samples were investigated. Superconducting properties of the polymer ceramic nanocomposites are explained by intercalation of macromolecule fragments into the interstitial layer of the ceramics’ grains. This phenomenon leads to a change in the morphological structure of the superconducting nanocomposites.

Computational simulation of subatomic-resolution AFM and STM images for graphene/hexagonal boron nitride heterostructures with intercalated defects

NASA Astrophysics Data System (ADS)

Lee, Junsu; Kim, Minjung; Chelikowsky, James R.; Kim, Gunn

2016-07-01

Using ab initio density functional calculations, we predict subatomic-resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) images of vertical heterostructures of graphene/hexagonal boron nitride (h-BN) with an intercalated metal atom (Li, K, Cr, Mn, Co, or Cu), and study the effects of the extrinsic metal defect on the interfacial coupling. We find that the structural deformation of the graphene/h-BN layer caused by the metal defect strongly affects the AFM images, whereas orbital hybridization between the metal defect and the graphene/h-BN layer characterizes the STM images.

Rheological and electrical properties of hybrid nanocomposites of epoxy resins filled with graphite nanoplatelets and carbon black.

PubMed

Truong, Quang-Trung; Lee, Seon-Suk; Lee, Dai-Soo

2011-02-01

Graphite nanoplatelets (GNP) were prepared by microwave irradiation of natural graphites intercalated with ferric chloride in nitromethane (GIC). Intercalated structure of GIC was confirmed by X-ray diffraction patterns. SEM images of GIC after microwave irradiation showed the exfoliation of GIC, the formation of GNPs. Hybrid nanocomposites of bisphenol-A type epoxy resins filled with GNP and a conductive carbon black (CB) were prepared and rheological and electrical properties of the nanocomposites were investigated. Viscosity and electrical surface resistivity of the nanocomposites showed minima at certain mixtures of GNP and CB in the epoxy resins.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

DOEpatents

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher; Lane, George Hamilton; Morgan, Dane; Nevin, Josh; Ceder, Gerbrand; Persson, Kristin Aslaug; Eaglesham, David

2015-10-27

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqeuous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negative electrode active material is described.

Onset of superconductivity in sodium and potassium intercalated molybdenum disulphide

NASA Technical Reports Server (NTRS)

Somoano, R. B.; Rembaum, A.

1971-01-01

Molybdenum disulfide in the form of natural crystals or powder has been intercalated at -65 to -70 C with sodium and potassium using the liquid ammonia technique. All intercalated samples were found to show a superconducting transition. A plot of the percent of diamagnetic throw versus temperature indicates the possible existence of two phases in the potassium intercalated molybdenum disulfide. The onset of superconductivity in potassium and sodium intercalated molybdenite powder was found to be approximately 6.2 and approximately 4.5 K, respectively. The observed superconductivity is believed to be due to an increase in electron density as a result of intercalation.

Environmental stability of intercalated graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, J. R.; Jaworske, D. A.

1985-01-01

Graphite fibers intercalated with bromine, iodine monochloride, ferric chloride, and cupric chloride were subjected to stability tests under four environments which are encountered by engineering materials in the aerospace industry: ambient laboratory conditions, as would be experienced during handling operations and terrestrial applications; high vacuum, as would be experienced in space applications; high humidity, as would be experienced in marine applications; and high temperature, as would be experienced in some processing steps and applications. Monitoring the resistance of the fibers at ambient laboratory conditions revealed that only the ferric chloride intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were stable for long periods under high vacuum. Ferric chloride, cupric chloride, and iodine monochloride intercalated fibers were sensitive to high humidity conditions. All intercalated fibers began to degrade above 250 C. The order of their thermal stability, from lowest to highest, was cupric chloride, iodine monochloride, bromine, and ferric chloride. Of the four types of intercalated fibers tested, the bromine intercalated fibers appear to have the most potential for application, based on environmental stability.

Highly Conductive and Transparent Large-Area Bilayer Graphene Realized by MoCl5 Intercalation.

PubMed

Kinoshita, Hiroki; Jeon, Il; Maruyama, Mina; Kawahara, Kenji; Terao, Yuri; Ding, Dong; Matsumoto, Rika; Matsuo, Yutaka; Okada, Susumu; Ago, Hiroki

2017-11-01

Bilayer graphene (BLG) comprises a 2D nanospace sandwiched by two parallel graphene sheets that can be used to intercalate molecules or ions for attaining novel functionalities. However, intercalation is mostly demonstrated with small, exfoliated graphene flakes. This study demonstrates intercalation of molybdenum chloride (MoCl 5 ) into a large-area, uniform BLG sheet, which is grown by chemical vapor deposition (CVD). This study reveals that the degree of MoCl 5 intercalation strongly depends on the stacking order of the graphene; twist-stacked graphene shows a much higher degree of intercalation than AB-stacked. Density functional theory calculations suggest that weak interlayer coupling in the twist-stacked graphene contributes to the effective intercalation. By selectively synthesizing twist-rich BLG films through control of the CVD conditions, low sheet resistance (83 Ω ▫ -1 ) is realized after MoCl 5 intercalation, while maintaining high optical transmittance (≈95%). The low sheet resistance state is relatively stable in air for more than three months. Furthermore, the intercalated BLG film is applied to organic solar cells, realizing a high power conversion efficiency. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

NASA Astrophysics Data System (ADS)

Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

2014-12-01

Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the lowest concentrations of CO2. Likewise,CH4 XRD showed indirect evidence of CO2 intercalation from an increase in the basal spacing from 11.8 to 12.3 under identical conditions. These findings demonstrate that water and CO2 intercalation processes could lead to permeability changes that directly impact methane transmissivity in shales.

Intercalation and de-intercalation pathway of proflavine through the minor and major grooves of DNA: roles of water and entropy.

PubMed

Sasikala, Wilbee D; Mukherjee, Arnab

2013-05-07

DNA intercalation is a clinically relevant biophysical process due to its potential to inhibit the growth and survival of tumor cells and microbes through the arrest of the transcription and replication processes. Extensive kinetic and thermodynamic studies have followed since the discovery of the intercalative binding mode. However, the molecular mechanism and the origin of the thermodynamic and kinetic profile of the process are still not clear. Here we have constructed the free energy landscape of intercalation, de-intercalation and dissociation from both the major and minor grooves of DNA using extensive all-atom metadynamics simulations, capturing both the free energy barriers and stability in close agreement with fluorescence kinetic experiments. In the intercalated state, an alternate orientation of proflavine is found with an almost equal stability compared to the crystal orientation, however, separated by a 5.0 kcal mol(-1) barrier that decreases as the drug approaches the groove edges. This study provides a comprehensive picture in comparison with experiments, which indicates that the intercalation and de-intercalation of proflavine happen through the major groove side, although the effective intercalation barrier increases because the path of intercalation goes through the stable (abortive) minor groove bound state, making the process a millisecond long one in excellent agreement with the experiments. The molecular origin of the higher barrier for the intercalation from the minor groove side is attributed to the desolvation energy of DNA and the loss of entropy, while the barrier from the major groove, in the absence of desolvation energy, is primarily entropic.

Reshaping the Energy Landscape Transforms the Mechanism and Binding Kinetics of DNA Threading Intercalation.

PubMed

Clark, Andrew G; Naufer, M Nabuan; Westerlund, Fredrik; Lincoln, Per; Rouzina, Ioulia; Paramanathan, Thayaparan; Williams, Mark C

2018-02-06

Molecules that bind DNA via threading intercalation show high binding affinity as well as slow dissociation kinetics, properties ideal for the development of anticancer drugs. To this end, it is critical to identify the specific molecular characteristics of threading intercalators that result in optimal DNA interactions. Using single-molecule techniques, we quantify the binding of a small metal-organic ruthenium threading intercalator (Δ,Δ-B) and compare its binding characteristics to a similar molecule with significantly larger threading moieties (Δ,Δ-P). The binding affinities of the two molecules are the same, while comparison of the binding kinetics reveals significantly faster kinetics for Δ,Δ-B. However, the kinetics is still much slower than that observed for conventional intercalators. Comparison of the two threading intercalators shows that the binding affinity is modulated independently by the intercalating section and the binding kinetics is modulated by the threading moiety. In order to thread DNA, Δ,Δ-P requires a "lock mechanism", in which a large length increase of the DNA duplex is required for both association and dissociation. In contrast, measurements of the force-dependent binding kinetics show that Δ,Δ-B requires a large DNA length increase for association but no length increase for dissociation from DNA. This contrasts strongly with conventional intercalators, for which almost no DNA length change is required for association but a large DNA length change must occur for dissociation. This result illustrates the fundamentally different mechanism of threading intercalation compared with conventional intercalation and will pave the way for the rational design of therapeutic drugs based on DNA threading intercalation.

Effects of preparation methods on the structure and mechanical properties of wet conditioned starch/montmorillonite nanocomposite films.

PubMed

Müller, Péter; Kapin, Éva; Fekete, Erika

2014-11-26

TPS/Na-montmorillonite nanocomposite films were prepared by solution and melt blending. Clay content changed between 0 and 25 wt% based on the amount of dry starch. Structure, tensile properties, and water content of wet conditioned films were determined as a function of clay content. Intercalated structure and VH-type crystallinity of starch were found for all the nanocomposites independently of clay and plasticizer content or preparation method, but at larger than 10 wt% clay content nanocomposites prepared by melt intercalation contained aggregated particles as well. In spite of the incomplete exfoliation clay reinforces TPS considerably. Preparation method has a strong influence on mechanical properties of wet conditioned films. Mechanical properties of the conditioned samples prepared by solution homogenization are much better than those of nanocomposites prepared by melt blending. Water, which was either adsorbed or bonded in the composites in conditioning or solution mixing process, respectively, has different effect on mechanical properties. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sodium intercalation in the phosphosulfate cathode NaFe2(PO4)(SO4)2

NASA Astrophysics Data System (ADS)

Ben Yahia, Hamdi; Essehli, Rachid; Amin, Ruhul; Boulahya, Khalid; Okumura, Toyoki; Belharouak, Ilias

2018-04-01

The compound NaFe2(PO4)(SO4)2 is successfully synthesized via a solid state reaction route and its crystal structure is determined using powder X-ray diffraction data. NaFe2(PO4)(SO4)2 phase is also characterized by cyclic voltammetry, galvanostatic cycling and electrochemical impedance spectroscopy. NaFe2(PO4)(SO4)2 crystallizes with the well-known NASICON-type structure. SAED and HRTEM experiments confirm the structural model, and no ordering between the PO4-3 and SO4-2 polyanions is detected. The electrochemical tests indicate that NaFe2(PO4)(SO4)2 is a 3 V sodium intercalating cathode. The electrical conductivity is relatively low (2.2 × 10-6 Scm-1 at 200 °C) and the obtained activation energy is ∼0.60eV. The GITT experiments indicate that the diffusivity values are in the range of 10-11-10-12 cm2/s within the measured sodium concentrations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tripathi, S.; Zhang, D.; Paukstelis, P. J.

DNA has proved to be an excellent material for nanoscale construction because complementary DNA duplexes are programmable and structurally predictable. However, in the absence of Watson–Crick pairings, DNA can be structurally more diverse. Here, we describe the crystal structures of d(ACTCGGATGAT) and the brominated derivative, d(AC BrUCGGA BrUGAT). These oligonucleotides form parallel-stranded duplexes with a crystallographically equivalent strand, resulting in the first examples of DNA crystal structures that contains four different symmetric homo base pairs. Two of the parallel-stranded duplexes are coaxially stacked in opposite directions and locked together to form a tetraplex through intercalation of the 5'-most A–A basemore » pairs between adjacent G–G pairs in the partner duplex. The intercalation region is a new type of DNA tertiary structural motif with similarities to the i-motif. 1H– 1H nuclear magnetic resonance and native gel electrophoresis confirmed the formation of a parallel-stranded duplex in solution. Finally, we modified specific nucleotide positions and added d(GAY) motifs to oligonucleotides and were readily able to obtain similar crystals. This suggests that this parallel-stranded DNA structure may be useful in the rational design of DNA crystals and nanostructures.« less

Effective Interlayer Engineering of Two-Dimensional VOPO4 Nanosheets via Controlled Organic Intercalation for Improving Alkali Ion Storage.

PubMed

Peng, Lele; Zhu, Yue; Peng, Xu; Fang, Zhiwei; Chu, Wangsheng; Wang, Yu; Xie, Yujun; Li, Yafei; Cha, Judy J; Yu, Guihua

2017-10-11

Two-dimensional (2D) energy materials have shown the promising electrochemical characteristics for lithium ion storage. However, the decreased active surfaces and the sluggish charge/mass transport for beyond-lithium ion storage that has potential for large-scale energy storage systems, such as sodium or potassium ion storage, caused by the irreversible restacking of 2D materials during electrode processing remain a major challenge. Here we develop a general interlayer engineering strategy to address the above-mentioned challenges by using 2D ultrathin vanadyl phosphate (VOPO 4 ) nanosheets as a model material for challenging sodium ion storage. Via controlled intercalation of organic molecules, such as triethylene glycol and tetrahydrofuran, the sodium ion transport in VOPO 4 nanosheets has been significantly improved. In addition to advanced characterization including X-ray diffraction, high-resolution transmission electron microscopy, and X-ray absorption fine structure to characterize the interlayer and the chemical bonding/configuration between the organic intercalants and the VOPO 4 host layers, density functional theory calculations are also performed to understand the diffusion behavior of sodium ions in the pure and TEG intercalated VOPO 4 nanosheets. Because of the expanded interlayer spacing in combination with the decreased energy barriers for sodium ion diffusion, intercalated VOPO 4 nanosheets show much improved sodium ion transport kinetics and greatly enhanced rate capability and cycling stability for sodium ion storage. Our results afford deeper understanding of the interlayer-engineering strategy to improve the sodium ion storage performance of the VOPO 4 nanosheets. Our results may also shed light on possible multivalent-ion based energy storage such as Mg 2+ and Al 3+ .

Development of propidium iodide as a fluorescence probe for the on-line screening of non-specific DNA-intercalators in Fufang Banbianlian Injection.

PubMed

Niu, Yanyan; Li, Sensen; Lin, Zongtao; Liu, Meixian; Wang, Daidong; Wang, Hong; Chen, Shizhong

2016-09-09

Fufang Banbianlian Injection (FBI) has been widely used as an anti-inflammatory and anti-tumor prescription. To understand the relationships between its bioactive ingredients and pharmacological efficacies, our previous study has been successfully identified some DNA-binding compounds in FBI using an established on-line screening system, in which 4',6-diamidino-2-phenylindole (DAPI) was developed as a probe. However, DAPI can be only used to screen ATT-specific DNA minor groove binders, leaving the potential active intercalators unknown in FBI. As a continuation of our studies on FBI, here we present a sensitive analytical method for rapid identification and evaluation of DNA-intercalators using propidium iodide (PI) as a fluorescent probe. We have firstly established the technique of high-performance liquid chromatography-diode-array detector-multistage mass spectrometry-deoxyribonucleic acid-propidium iodide-fluorescence detector (HPLC-DAD-MS(n)-DNA-PI-FLD) system. As a result, 38 of 58 previously identified compounds in FBI were DNA-intercalation active. Interestingly, all previously reported DNA-binders also showed intercalative activities, suggesting they are dual-mode DNA-binders. Quantitative study showed that flavonoid glycosides and chlorogenic acids were the main active compounds in FBI, and displayed similar DNA-binding ability using either DAPI or PI. In addition, 13 active compounds were used to establish the structure-activity relationships. In this study, PI was developed into an on-line method for identifying DNA-intercalators for the first time, and thus it will be a useful high-throughput screening technique for other related samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Effectiveness of Co intercalation between Graphene and Ir(1 1 1)

NASA Astrophysics Data System (ADS)

Carlomagno, I.; Drnec, J.; Scaparro, A. M.; Cicia, S.; Mobilio, S.; Felici, R.; Meneghini, C.

2018-04-01

Graphene can be used to avoid the oxidation of metallic films. This work explores the effectiveness of such stabilizing effect on Cobalt (Co) films intercalated between Graphene and Ir(1 1 1). After intercalation at 300 °C, two Co films are exposed to ambient pressure and investigated using Co-K edge X-ray Absorption Near Edge Spectroscopy. The formation of a disordered oxide phase is observed, and associated to the presence of some non-intercalated Co. Further annealing at 500 °C causes the oxide reduction to metallic Co which further intercalates below the Graphene. Once the intercalation is completed, Graphene prevents the Co from oxidation under ambient pressure conditions.

Molecular Simulation Models of Carbon Dioxide Intercalation in Hydrated Sodium Montmorillonite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Myshakin, Evgeniy; Saidi, Wissam; Romanov, Vyacheslav

2016-11-22

In this study, classical molecular dynamics simulations and density functional theory (DFT)-based molecular dynamics are used to elucidate the process of CO 2 intercalation into hydrated Na-montmorillonite at P-T conditions relevant to geological formations suitable for CO 2 storage. Of particular interest are the structural and transport properties of interlayer species after CO 2 intercalation. The conducted simulations allowed the research team to quantify expansion/contraction of smectite as a function of CO 2 and H 2O compositions. The resulting swelling curves can be used to gauge the amount of stored CO 2, compare it to the experiment, and estimate changesmore » in geomechanical properties of the storage formation. The obtained results showed that the infrared signal of the asymmetric stretch vibration of CO 2 molecule is extremely sensitive to the solvent environment. The extent of the frequency shift relative to the gas-phase value can be used to probe hydration level in the interlayer with intercalated CO 2. Interaction of supercritical CO 2 with brine in deep geological formations promotes an increase of hydrophobicity of clay surfaces. As a result of wettability alteration, estimated diffusion constants of CO 2 and H 2O increase with the increased CO 2 load; this can contribute to faster migration of CO 2 throughout the formation.« less

Reconstruction de la surface de Fermi dans l'etat normal d'un supraconducteur a haute Tc: Une etude du transport electrique en champ magnetique intense

NASA Astrophysics Data System (ADS)

Le Boeuf, David

Des mesures de resistance longitudinale et de resistance de Hall en champ magnetique intense transverse (perpendiculaire aux plans CuO2) ont ete effectuees au sein de monocristaux de YBa2Cu3Oy (YBCO) demacles, ordonnes et de grande purete, afin d'etudier l'etat fondamental des supraconducteurs a haute Tc dans le regime sous-dope. Cette etude a ete realisee en fonction du dopage et de l'orientation du courant d'excitation J par rapport a l'axe orthorhombique b de la structure cristalline. Les mesures en champ magnetique intense revelent par suppression de la supraconductivite des oscillations magnetiques des resistances longitudinale et de Hall dans YBa2Cu 3O6.51 et YBa2Cu4O8. La conformite du comportement de ces oscillations quantiques au formalisme de Lifshitz-Kosevich, apporte la preuve de l'existence d'une surface de Fermi fermee a caractere quasi-2D, abritant des quasiparticules coherentes respectant la statistique de Fermi-Dirac, dans la phase pseudogap d'YBCO. La faible frequence des oscillations quantiques, combinee avec l'etude de la partie monotone de la resistance de Hall en fonction de la temperature indique que la surface de Fermi d'YBCO sous-dope comprend une petite poche de Fermi occupee par des porteurs de charge negative. Cette particularite de la surface de Fermi dans le regime sous-dope incompatible avec les calculs de structure de bande est en fort contraste avec la structure electronique presente dans le regime surdope. Cette observation implique ainsi l'existence d'un point critique quantique dans le diagramme de phase d'YBCO, au voisinage duquel la surface de Fermi doit subir une reconstruction induite par l'etablissement d'une brisure de la symetrie de translation du reseau cristallin sous-jacent. Enfin, l'etude en fonction du dopage de la resistance de Hall et de la resistance longitudinale en champ magnetique intense suggere qu'un ordre du type onde de densite (DW) est responsable de la reconstruction de la surface de Fermi. L'analogie de la phenomenologie entourant le comportement des resistances longitudinale et de Hall dans YBa2Cu3Oy, avec des systemes dans lesquels l'existence d'un ordre du type DW est etablie, notamment des cuprates a structure tetragonale a basse temperature ("Low Temperature Tetragonal", LTT), indique que l'ordre causant la reconstruction de la surface de Fermi est stabilise au voisinage du dopage p = 1/8, et est en competition directe avec la supraconductivite.

Is it intelligent to intercalate? A two centre cross-sectional study exploring the value of intercalated degrees, and the possible effects of the recent tuition fee rise in England

PubMed Central

Stubbs, Timothy Alan; Lightman, Elewys G; Mathieson, Peter

2013-01-01

Aims and objectives To explore the value of intercalated degrees, including student perceptions and academic sequelae. To gauge the likely effect of the recent tuition fee rise and to identify any differences in intercalated degrees between Bristol and Sheffield universities. Design Cross-sectional study using questionnaires. Setting Bristol and Sheffield Medical Schools, UK. Participants 1484 medical students in their clinical years were e-mailed the questionnaire. 578 students responded: 291 from Bristol and 287 from Sheffield (n=578; mean age=22.41; SD 1.944; 38.9% male; 61.1% female). The response rate from previous intercalators was 52.5% from Bristol and 58.7% from Sheffield, while for non-intercalators it was 27.7% and 34.6%, respectively. Main outcome measures (1) Student preconceptions, opinions, results and academic sequelae from intercalated degrees at both centres. (2) Students’ attitudes concerning the effect of the increase in tuition fees. Results Those with clinical academic supervisors gained significantly more posters (p=0.0002) and publications (p<0.0001), and also showed a trend to gain more first class honours (p=0.055). Students at Sheffield had a significantly greater proportion of clinical academic supervisors than students at Bristol (p<0.0001). 89.2% said that an intercalated degree was the right decision for them; however, only 27.4% stated they would have intercalated if fees had been £9000 per annum. Conclusions Students clearly value intercalated degrees, feel they gained a substantial advantage over their peers as well as skills helpful for their future careers. The rise in tuition fees is likely to reduce the number of medical students opting to undertake an intercalated degree, and could result in a further reduction in numbers following an academic path. Sheffield University have more intercalating students supervised by clinical academics. Clinical academics appear more effective as supervisors for medical students undertaking an intercalated degree in terms of results and additional academic sequelae. PMID:23355672

A Novel Battery Cathode Material Based on intercalation Chemistry: Redox Reactions of the 2,5-Dimercapto-1,3,4-Thiadiazole/V2O5 Xerogel System

DTIC Science & Technology

1998-06-29

of some interstitial water during intercalation of the disulfide polymer of DMcT. Elemental analysis gives a composition for the intercalation...the disulfide polymer of DMcT. Elemental analysis gives a composition for the intercalation material of [(polyDMcT)o25*V205𔃻.4H20]. The cyclic...13.5 A). This change is consistent with loss of some interstitial water during intercalation of the disulfide polymer of DMcT. Elemental analysis

Structural evolution of Li{sub x}Mn{sub 2}O{sub 4} in lithium-ion battery cells measured in situ using synchrotron X-ray diffraction techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukerjee, S.; Thurston, T.R.; Jisrawi, N.M.

The authors describe synchrotron based X-ray diffraction techniques and issues related to in situ studies of intercalation processes in battery electrodes. They then demonstrate the utility of this technique, through a study of two batches of Li{sub x}Mn{sub 2}O{sub 4} cathode materials. The structural evolution of these spinel materials was monitored in situ during the initial charge of these electrodes in actual battery cells. Significant differences were observed in the two batches, particularly in the intercalation range of x = 0.45 to 0.20. The first-order structural transitions in this region indicated coexistence of two cubic phases in the batch 2more » material, whereas the batch 1 material showed suppressed two-phase coexistence. Batch 2 cells also indicated structural evolution in the low-potential region below 3.0 V in contrast to the batch 1 material. Differences in structural evolution between batches of Li{sub x}Mn{sub 2}O{sub 4} could have important ramifications in their cycle life and stability characteristics.« less

Multi-Anion Intercalated Layered Double Hydroxide Nanosheet-Assembled Hollow Nanoprisms with Improved Pseudocapacitive and Electrocatalytic Properties.

PubMed

Li, Zhengping; Han, Fangchun; Li, Cheng; Jiao, Xiuling; Chen, Dairong

2018-05-04

Electrochemically active hollow nanostructured materials hold great promise in diverse energy conversion and storage applications, however, intricate synthesis steps and poor control over compositions and morphologies have limited the realization of delicate hollow structures with advanced functional properties. In this study, we demonstrate a one-step wet-chemical strategy for co-engineering the hollow nanostructure and anion intercalation of nickel cobalt layered double hydroxide (NiCo-LDH) to attain highly electrochemical active energy conversion and storage functionalities. Self-templated pseudomorphic transformation of cobalt acetate hydroxide solid nanoprisms using nickel nitrate leads to the construction of well-defined NiCo-LDH hollow nanoprisms (HNPs) with multi-anion intercalation. The unique hierarchical nanosheet-assembled hollow structure and efficiently expanded interlayer spacing offer an increased surface area and exposure of active sites, reduced mass and charge transfer resistance, and enhanced stability of the materials. This leads to a significant improvement in the pseudocapacitive and electrocatalytic properties of NiCo-LDH HNP with respect to specific capacitance, rate and cycling performance, and OER overpotential, outperforming most of the recently reported NiCo-based materials. This work establishes the potential of manipulating sacrificial template transformation for the design and fabrication of novel classes of functional materials with well-defined nanostructures for electrochemical applications and beyond. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Excitation and characterization of image potential state electrons on quasi-free-standing graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yi; Li, Yunzhe; Sadowski, Jerzy T.

We investigate the band structure of image potential states in quasi-free-standing graphene (QFG) monolayer islands using angle-resolved two-photon-photoemission spectroscopy. Direct probing by low-energy electron diffraction shows that QFG is formed following oxygen intercalation into the graphene-Ir(111) interface. Despite the apparent decoupling of the monolayer graphene from the Ir substrate, we find that the binding energy of the n = 1 image potential state on these QFG islands increases by 0.17 eV, as compared to the original Gr/Ir(111) interface. We use calculations based on density-functional theory to construct an empirical, one-dimensional potential that quantitatively reproduces the image potential state binding energymore » and links the changes in the interface structure to the shift in energy. Specifically, two factors contribute comparably to this energy shift: a deeper potential well arising from the presence of intercalated oxygen adatoms and a wider potential well associated with the increase in the graphene-Ir distance. While image potential states have not been observed previously on QFG by photoemission, our paper now demonstrates that they may be strongly excited in a well-defined QFG system produced by oxygen intercalation. Finally, this opens an opportunity for studying the surface electron dynamics in QFG systems, beyond those found in typical nonintercalated graphene-on-substrate systems.« less

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Production of thick uniform-coating films containing rectorite on nanofibers through the use of an automated coating machine.

PubMed

Wu, Yang; Li, Xueyong; Shi, Xiaowen; Zhan, Yingfei; Tu, Hu; Du, Yumin; Deng, Hongbing; Jiang, Linbin

2017-01-01

When an efficient automated coating machine is used to process layer-by-layer (LBL) deposited nanofibrous mats, it causes an obvious planar effect on the surface of the mats, which can be eliminated through ultimate immersion. During this process, chitosan (CS) - rectorite (REC) intercalated composite films are built on the surface of cellulose acetate (CA) nanofibrous mats by a coating machine. Then, the immersion process is utilized to allow positively charged CS or CS-REC intercalated composites to uniformly assemble on the surface of negatively charged CA nanofibers. An investigation into the morphology of the resultant scaffolds confirms that the uniquely small pore size, high specific surface area and typically three-dimensional (3D) structure of nanofibrous mats remain present. The results of Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) indicate that it is feasible to assemble nanofibrous mats using a coating machine. The intercalated structure of CS-REC is confirmed by the results of small-angle X-ray diffraction (SAXRD) and wide-angle X-ray diffraction (WAXRD). The results of the cell experiment and antibacterial test demonstrate that the addition of REC not only has little impact on the cytocompatibility of the mats but also enhances their ability to inhibit bacteria. Copyright © 2016 Elsevier B.V. All rights reserved.

Excitation and characterization of image potential state electrons on quasi-free-standing graphene

DOE PAGES

Lin, Yi; Li, Yunzhe; Sadowski, Jerzy T.; ...

2018-04-09

We investigate the band structure of image potential states in quasi-free-standing graphene (QFG) monolayer islands using angle-resolved two-photon-photoemission spectroscopy. Direct probing by low-energy electron diffraction shows that QFG is formed following oxygen intercalation into the graphene-Ir(111) interface. Despite the apparent decoupling of the monolayer graphene from the Ir substrate, we find that the binding energy of the n = 1 image potential state on these QFG islands increases by 0.17 eV, as compared to the original Gr/Ir(111) interface. We use calculations based on density-functional theory to construct an empirical, one-dimensional potential that quantitatively reproduces the image potential state binding energymore » and links the changes in the interface structure to the shift in energy. Specifically, two factors contribute comparably to this energy shift: a deeper potential well arising from the presence of intercalated oxygen adatoms and a wider potential well associated with the increase in the graphene-Ir distance. While image potential states have not been observed previously on QFG by photoemission, our paper now demonstrates that they may be strongly excited in a well-defined QFG system produced by oxygen intercalation. Finally, this opens an opportunity for studying the surface electron dynamics in QFG systems, beyond those found in typical nonintercalated graphene-on-substrate systems.« less

Visualization of drug-nucleic acid interactions at atomic resolution v. structure of two aminoacridine/dinucleoside monophosphate crystalline complexes, proflavine: 5-iodocytidylyl(3'-5') guanosine and acridine orange: 5-iodocytidylyl(3'-5') guanosine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddy, B.S.; Seshadri, T.P.; Sakore, T.D.

1979-01-01

Acridine orange and proflavine form complexes with the dinucleoside monophosphate, 5-iodocytidylyl(3'-5') guanosine (iodoCpG). The acridine orange-iodoCpG crystals are monoclinic, space group P2/sub 1/, with unit cell dimensions a = 14.36 A, b = 19.64 A, c = 20.67 A, ..beta.. = 102.5. The proflavine-iodoCpG crystals are monoclinic, space group C2, with unit cell dimensions a = 32.14 A, b = 22.23 A, c = 18.42 A, ..beta.. = 123.3. Both structures have been solved to atomic resolution by Patterson and Fourier methods, and refined by full matrix least squares. Acridine orange forms an intercalative structure with iodoCpG but the acridinemore » nucleus lies asymmetrically in the intercalation site. This asymmetric intercalation is accompanied by a sliding of base-pairs upon the acridine nucleus. Base-pairs above and below the drug are separated by about 6.8 A and are twisted about 10/sup 0/. Proflavine demonstrates symmetric intercalation with iodoCpG. Hydrogen bonds connect amino- groups on proflavine with phosphate oxygen atoms on the dinucleotide. Base-pairs above and below the intercalative proflavine molecule are twisted about 36/sup 0/. The altered magnitude of this angular twist reflects the sugar puckering pattern that is observed. We propose a proflavine-DNA and an acridine orange-DNA binding model. We will describe these models in detail in this paper.« less

Ultrastructural changes in cardiac myocytes from Boxer dogs with arrhythmogenic right ventricular cardiomyopathy

PubMed Central

Oxford, Eva M.; Danko, Charles G.; Kornreich, Bruce G.; Maass, Karen; Hemsley, Shari A.; Raskolnikov, Dima; Fox, Philip R.; Delmar, Mario; Moïse, N. Sydney

2011-01-01

Objectives We sought to quantify the number and length of desmosomes, gap junctions, and adherens junctions in arrhythmogenic right ventricular cardiomyopathy (ARVC) and non-ARVC dogs, and to determine if ultrastructural changes existed. Animals Hearts from 8 boxer dogs afflicted with histopathologically confirmed ARVC and 6 dogs without ARVC were studied. Methods Quantitative transmission electron microscopy (TEM) and Western blot semi-quantification of α-actinin were used to study the intercalated disc and sarcomere of the right and left ventricles. Results When ARVC dogs were compared to non-ARVC dogs reductions in the number of desmosomes (P = 0.04), adherens junctions (P = 0.04) and gap junctions (P = 0.02) were found. The number of gap junctions (P = 0.04) and adherens junctions (P = 0.04) also were reduced in the left ventricle, while the number of desmosomes was not (P = 0.88). A decrease in the length of desmosomal complexes within LV samples (P=0.04) was found. These findings suggested disruption of proteins providing attachment of the cytoskeleton to the intercalated disc. Immunoblotting did not demonstrate a quantitative reduction in the amount of α-actinin in ARVC afflicted samples. All boxers with ARVC demonstrated the presence of electron dense material originating from the Z band and extending into the sarcomere, apparently at the expense of the cytoskeletal structure. Conclusions These results emphasize the importance of structural integrity of the intercalated disc in the pathogenesis of ARVC. In addition, observed abnormalities in sarcomeric structure suggest a novel link between ARVC and the actin-myosin contractile apparatus. PMID:21636338

Unveiling the Mode of Interaction of Berberine Alkaloid in Different Supramolecular Confined Environments: Interplay of Surface Charge between Nano-Confined Charged Layer and DNA.

PubMed

Kundu, Niloy; Roy, Arpita; Banik, Debasis; Sarkar, Nilmoni

2016-02-18

In this Article, we demonstrate a detailed characterization of binding interaction of berberine chloride (BBCl) with calf-thymus DNA (CT-DNA) in buffer solution as well as in two differently charged reverse micelles (RMs). The photophyscial properties of this alkaloid have been modulated within these microheterogeneous bioassemblies. The mode of binding of this alkaloid with DNA is of debate to date. However, fluorescence spectroscopic measurements, circular dichroism (CD) measurement, and temperature-dependent study unambiguously establish that BBCl partially intercalates into the DNA base pairs. The nonplanarity imposed by partial saturation in their structure causes the nonclassical types of intercalation into DNA. Besides the intercalation, electrostatic interactions also play a significant role in the binding between BBCl and DNA. DNA structure turns into a condensed form after encapsulation into RMs, which is followed by the CD spectra and microscopy study. The probe location and dynamics in the nanopool of the RMs depended on the electrostatic interaction between the charged surfactants and cationic berberine. The structural alteration of CT-DNA from B form to condensed form and the interplay of surface charge between RMs and DNA determine the interaction between the alkaloid and DNA in RMs. Time-resolved study and fluorescence anisotropy measurements successfully provide the binding interaction of BBCl in the nanopool of the RMs in the absence and in the presence of DNA. This study motivates us to judge further the potential applicability of this alkaloid in other biological systems or other biomimicking organized assemblies.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doe, Robert E.; Downie, Craig M.; Fischer, Christopher

2016-01-19

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqueous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negativemore » electrode active material is described.« less

Evidences for dry deintercalation in layered compounds upon controlled surface charging in x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Feldman, Y.; Zak, A.; Tenne, R.; Cohen, H.

2003-09-01

Pronounced surface diffusion is observed during x-ray photoelectron spectroscopy measurements of 2H platelets and inorganic fullerene-like (IF) MS2 (M=W,Mo) powders, intercalated with alkaline (A=K,Na) elements. Using controlled surface charging the intercalants migrate towards the surface, where they oxidize. This dry deintercalation is controllable via external charging parameters, yet showing that internal chemical and structural parameters play an important role in the process. Diffusion rates out of 2H matrixes are generally higher than in corresponding IF samples. Clear differences are also found between Mo and W-based systems. Application of this approach into surface modification and processing is proposed.

Layered transition metal carboxylates: efficient reusable heterogeneous catalyst for epoxidation of olefins.

PubMed

Sen, Rupam; Bhunia, Susmita; Mal, Dasarath; Koner, Subratanath; Miyashita, Yoshitaro; Okamoto, Ken-Ichi

2009-12-01

Layered metal carboxylates [M(malonato)(H(2)O)(2)](n) (M = Ni(II) and Mn(II)) that have a claylike structure have been synthesized hydrothermally and characterized. The interlayer separation in these layered carboxylates is comparable to that of the intercalation distance of the naturally occurring clay materials or layered double hydroxides (LDHs). In this study, we have demonstrated that, instead of intercalating the metal complex into layers of the clay or LDH, layered transition metal carboxylates, [M(malonato)(H(2)O)(2)](n), as such can be used as a recyclable heterogeneous catalyst in olefin epoxidation reaction. Metal carboxylates [M(malonato)(H(2)O)(2)](n) exhibit excellent catalytic performance in olefin epoxidation reaction.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher

2016-07-26

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqueous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negativemore » electrode active material is described.« less

Optical determination of the electronic coupling and intercalation geometry of thiazole orange homodimer in DNA

NASA Astrophysics Data System (ADS)

Cunningham, Paul D.; Bricker, William P.; Díaz, Sebastián A.; Medintz, Igor L.; Bathe, Mark; Melinger, Joseph S.

2017-08-01

Sequence-selective bis-intercalating dyes exhibit large increases in fluorescence in the presence of specific DNA sequences. This property makes this class of fluorophore of particular importance to biosensing and super-resolution imaging. Here we report ultrafast transient anisotropy measurements of resonance energy transfer (RET) between thiazole orange (TO) molecules in a complex formed between the homodimer TOTO and double-stranded (ds) DNA. Biexponential homo-RET dynamics suggest two subpopulations within the ensemble: 80% intercalated and 20% non-intercalated. Based on the application of the transition density cube method to describe the electronic coupling and Monte Carlo simulations of the TOTO/dsDNA geometry, the dihedral angle between intercalated TO molecules is estimated to be 81° ± 5°, corresponding to a coupling strength of 45 ± 22 cm-1. Dye intercalation with this geometry is found to occur independently of the underlying DNA sequence, despite the known preference of TOTO for the nucleobase sequence CTAG. The non-intercalated subpopulation is inferred to have a mean inter-dye separation distance of 19 Å, corresponding to coupling strengths between 0 and 25 cm-1. This information is important to enable the rational design of energy transfer systems that utilize TOTO as a relay dye. The approach used here is generally applicable to determining the electronic coupling strength and intercalation configuration of other dimeric bis-intercalators.

Evaluation and optimization of the conditions for an improved ferulic acid intercalation into a synthetic lamellar anionic clay.

PubMed

Schoubben, Aurélie; Blasi, Paolo; Giovagnoli, Stefano; Nocchetti, Morena; Ricci, Maurizio; Perioli, Luana; Rossi, Carlo

2006-03-01

The aim of the study is to optimize the intercalation conditions of ferulic acid (FERH), an antioxidant compound, into Mg-Al-hydrotalcite for a safe skin photoprotection. The intercalation products were prepared incubating hydrotalcite (HTlc) in aqueous solutions of FERH sodium salt at different temperatures over 4 and 8 days. Quantitative determination of intercalated FERH was performed by thermogravimetric analysis and morphology by scanning electron microscopy (SEM). FERH stability study was carried out at different pHs and temperatures. FERH was analyzed by reversed phase-high-performance liquid chromatography. Response surface methods (RSMs) were used to assess optimal intercalation conditions and FERH stability. In all intercalation products, FERH content was found to be about 48% w/w except when the intercalation process was carried out at 52 degrees C for 8 days and at 60 degrees C for both 4 and 8 days, which resulted to be 40.39, 39.99, and 34.99%, respectively. The RSM designs showed that intercalation improvement can be achieved by working at pH 6, at temperatures below 40 degrees C, and over 4 days of incubation. The optimal conditions for a proper FERH intercalation were assessed. The development of a new optimized protocol may improve HTlc-FER complex performances and safety by augmenting dosage and reducing the presence of harmful reactive species in the final formulation.

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

NASA Astrophysics Data System (ADS)

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.

Electrochemical Control of Copper Intercalation into Nanoscale Bi 2Se 3

DOE PAGES

Zhang, Jinsong; Sun, Jie; Li, Yanbin; ...

2017-02-20

Intercalation of exotic atoms or molecules into the layered materials remains an extensively investigated subject in current physics and chemistry. However, traditionally melt-growth and chemical interaction strategies are either limited by insufficiency of intercalant concentrations or destitute of accurate controllability. Here, we have developed a general electrochemical intercalation method to efficaciously regulate the concentration of zerovalent copper atoms into layered Bi 2Se 3, followed by comprehensive experimental characterization and analyses. Up to 57% copper atoms (Cu 6.7Bi 2Se 3) can be intercalated with no disruption to the host lattice. Meanwhile the unconventional resistance dip accompanied by a hysteresis loop belowmore » 40 K, as well as the emergence of new Raman peak in Cu xBi 2Se 3, is a distinct manifestation of the interplay between intercalated Cu atoms with Bi 2Se 3 host. Furthermore, our work demonstrates a new methodology to study fundamentally new and unexpected physical behaviors in intercalated metastable materials.« less

Synthesis and Characterization of Highly Intercalated Graphite Bisulfate

NASA Astrophysics Data System (ADS)

Salvatore, Marcella; Carotenuto, Gianfranco; De Nicola, Sergio; Camerlingo, Carlo; Ambrogi, Veronica; Carfagna, Cosimo

2017-03-01

Different chemical formulations for the synthesis of highly intercalated graphite bisulfate have been tested. In particular, nitric acid, potassium nitrate, potassium dichromate, potassium permanganate, sodium periodate, sodium chlorate, and hydrogen peroxide have been used in this synthesis scheme as the auxiliary reagent (oxidizing agent). In order to evaluate the presence of delamination, and pre-expansion phenomena, and the achieved intercalation degree in the prepared samples, the obtained graphite intercalation compounds have been characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD), infrared spectroscopy (FT-IR), micro-Raman spectroscopy ( μ-RS), and thermal analysis (TGA). Delamination and pre-expansion phenomena were observed only for nitric acid, sodium chlorate, and hydrogen peroxide, while the presence of strong oxidizers (KMnO4, K2Cr2O7) led to stable graphite intercalation compounds. The largest content of intercalated bisulfate is achieved in the intercalated compounds obtained from NaIO4 and NaClO3.

Synthesis and Characterization of Highly Intercalated Graphite Bisulfate.

PubMed

Salvatore, Marcella; Carotenuto, Gianfranco; De Nicola, Sergio; Camerlingo, Carlo; Ambrogi, Veronica; Carfagna, Cosimo

2017-12-01

Different chemical formulations for the synthesis of highly intercalated graphite bisulfate have been tested. In particular, nitric acid, potassium nitrate, potassium dichromate, potassium permanganate, sodium periodate, sodium chlorate, and hydrogen peroxide have been used in this synthesis scheme as the auxiliary reagent (oxidizing agent). In order to evaluate the presence of delamination, and pre-expansion phenomena, and the achieved intercalation degree in the prepared samples, the obtained graphite intercalation compounds have been characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD), infrared spectroscopy (FT-IR), micro-Raman spectroscopy (μ-RS), and thermal analysis (TGA). Delamination and pre-expansion phenomena were observed only for nitric acid, sodium chlorate, and hydrogen peroxide, while the presence of strong oxidizers (KMnO 4 , K 2 Cr 2 O 7 ) led to stable graphite intercalation compounds. The largest content of intercalated bisulfate is achieved in the intercalated compounds obtained from NaIO 4 and NaClO 3 .

Methoxy-modified kaolinite as a novel carrier for high-capacity loading and controlled-release of the herbicide amitrole

PubMed Central

Tan, Daoyong; Yuan, Peng; Annabi-Bergaya, Faïza; Liu, Dong; He, Hongping

2015-01-01

Methoxy-modified kaolinite was used as a novel carrier for loading and release of the herbicide 3-amino-1,2,4-triazole, known as amitrole (abbreviated here as AMT). The methoxy modification made the interlayer space of the kaolinite available for AMT intercalation. The AMT loading content in methoxy-modified kaolinite reached up to 20.8 mass% (twice the loading content by unmodified kaolinite). About 48% of this amount is located in the interlayer space. The release profiles of the AMT fit with the modified Korsmeyer-Peppas model. Due to the diffusional restriction of the intercalated AMT by the lamellar structure of the kaolinite and the strong electrostatic attraction between the intercalated AMT and the kaolinite, a slow release of AMT from the methoxy-modified kaolinite was achieved. These results show that the methoxy-modification is a facile method to make the interlayer space of kaolinite available for hosting other guest molecules. The methoxy-modified kaolinite is a promising candidate for high-capacity loading and controlled-release of other molecules such as drugs, agrochemicals, and biochemicals. PMID:25747124

Water-Lubricated Intercalation in V2 O5 ·nH2 O for High-Capacity and High-Rate Aqueous Rechargeable Zinc Batteries.

PubMed

Yan, Mengyu; He, Pan; Chen, Ying; Wang, Shanyu; Wei, Qiulong; Zhao, Kangning; Xu, Xu; An, Qinyou; Shuang, Yi; Shao, Yuyan; Mueller, Karl T; Mai, Liqiang; Liu, Jun; Yang, Jihui

2018-01-01

Low-cost, environment-friendly aqueous Zn batteries have great potential for large-scale energy storage, but the intercalation of zinc ions in the cathode materials is challenging and complex. Herein, the critical role of structural H 2 O on Zn 2+ intercalation into bilayer V 2 O 5 ·nH 2 O is demonstrated. The results suggest that the H 2 O-solvated Zn 2+ possesses largely reduced effective charge and thus reduced electrostatic interactions with the V 2 O 5 framework, effectively promoting its diffusion. Benefited from the "lubricating" effect, the aqueous Zn battery shows a specific energy of ≈144 Wh kg -1 at 0.3 A g -1 . Meanwhile, it can maintain an energy density of 90 Wh kg -1 at a high power density of 6.4 kW kg -1 (based on the cathode and 200% Zn anode), making it a promising candidate for high-performance, low-cost, safe, and environment-friendly energy-storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quasi free-standing epitaxial graphene fabrication on 3C-SiC/Si(111)

NASA Astrophysics Data System (ADS)

Amjadipour, Mojtaba; Tadich, Anton; Boeckl, John J.; Lipton-Duffin, Josh; MacLeod, Jennifer; Iacopi, Francesca; Motta, Nunzio

2018-04-01

Growing graphene on SiC thin films on Si is a cheaper alternative to the growth on bulk SiC, and for this reason it has been recently intensively investigated. Here we study the effect of hydrogen intercalation on epitaxial graphene obtained by high temperature annealing on 3C-SiC/Si(111) in ultra-high vacuum. By using a combination of core-level photoelectron spectroscopy, low energy electron diffraction, and near-edge x-ray absorption fine structure (NEXAFS) we find that hydrogen saturates the Si atoms at the topmost layer of the substrate, leading to free-standing graphene on 3C-SiC/Si(111). The intercalated hydrogen fully desorbs after heating the sample at 850 °C and the buffer layer appears again, similar to what has been reported for bulk SiC. However, the NEXAFS analysis sheds new light on the effect of hydrogen intercalation, showing an improvement of graphene’s flatness after annealing in atomic H at 600 °C. These results provide new insight into free-standing graphene fabrication on SiC/Si thin films.

Methoxy-modified kaolinite as a novel carrier for high-capacity loading and controlled-release of the herbicide amitrole

NASA Astrophysics Data System (ADS)

Tan, Daoyong; Yuan, Peng; Annabi-Bergaya, Faïza; Liu, Dong; He, Hongping

2015-03-01

Methoxy-modified kaolinite was used as a novel carrier for loading and release of the herbicide 3-amino-1,2,4-triazole, known as amitrole (abbreviated here as AMT). The methoxy modification made the interlayer space of the kaolinite available for AMT intercalation. The AMT loading content in methoxy-modified kaolinite reached up to 20.8 mass% (twice the loading content by unmodified kaolinite). About 48% of this amount is located in the interlayer space. The release profiles of the AMT fit with the modified Korsmeyer-Peppas model. Due to the diffusional restriction of the intercalated AMT by the lamellar structure of the kaolinite and the strong electrostatic attraction between the intercalated AMT and the kaolinite, a slow release of AMT from the methoxy-modified kaolinite was achieved. These results show that the methoxy-modification is a facile method to make the interlayer space of kaolinite available for hosting other guest molecules. The methoxy-modified kaolinite is a promising candidate for high-capacity loading and controlled-release of other molecules such as drugs, agrochemicals, and biochemicals.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Yong; Lii-Rosales, A.; Zhou, Y.

Theory and stochastic lattice-gas modeling is developed for the formation of intercalated metal islands in the gallery between the top layer and the underlying layer at the surface of layered materials. Our model for this process involves deposition of atoms, some fraction of which then enter the gallery through well-separated pointlike defects in the top layer. Subsequently, these atoms diffuse within the subsurface gallery leading to nucleation and growth of intercalated islands nearby the defect point source. For the case of a single point defect, continuum diffusion equation analysis provides insight into the nucleation kinetics. However, complementary tailored lattice-gas modelingmore » produces a more comprehensive and quantitative characterization. We analyze the large spread in nucleation times and positions relative to the defect for the first nucleated island. We also consider the formation of subsequent islands and the evolution of island growth shapes. The shapes reflect in part our natural adoption of a hexagonal close-packed island structure. As a result, motivation and support for the model is provided by scanning tunneling microscopy observations of the formation of intercalated metal islands in highly-ordered pyrolytic graphite at higher temperatures.« less

Size dependence effect of carbon-based anode material on intercalation characteristics of Li-ion battery

NASA Astrophysics Data System (ADS)

Anwar, Miftahul; Jupri, Dwi Rahmat; Saraswati, Teguh Endah

2017-01-01

This work aims to study the effect of the different size of Li-ion battery anode during charging state. Carbon-Based nanomaterial using arc-discharge in a liquid which is much simpler and cheaper compared to other techniques, i.e., CVD, laser vaporization, etc. The experiment was performed using intermediate DC power supply (1300 W) to produce an arc, and commercial graphite pencils (with 5 mm diameter) as negative and positive electrodes. Deionized water mixed with ethanol was used as a heat absorber. The result shows that arc discharge in deionized water could effectively produce carbon nanomaterial (i.e., nano-onions). In addition, finite element method-based simulation of the different intercalating process of Li-ion to the different shape of the anode, i.e., bulk semi-porous and porous anode materials for battery application is also presented. The results show that intercalation of Li ions depends on the anode structure due to the different potential density at anode region. This finding will provide support for design of Li-ion battery based on carbon nanomaterial

Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems

DOE PAGES

Martinez, Ulises; Dumont, Joseph H.; Holby, Edward F.; ...

2016-03-18

Graphitic materials are very essential in energy conversion and storage because of their excellent chemical and electrical properties. The strategy for obtaining functional graphitic materials involves graphite oxidation and subsequent dissolution in aqueous media, forming graphene-oxide nanosheets (GNs). Restacked GNs contain substantial intercalated water that can react with heteroatom dopants or the graphene lattice during reduction. We demonstrate that removal of intercalated water using simple solvent treatments causes significant structural reorganization, substantially affecting the oxygen reduction reaction (ORR) activity and stability of nitrogen-doped graphitic systems. Amid contrasting reports describing the ORR activity of GN-based catalysts in alkaline electrolytes, we demonstratemore » superior activity in an acidic electrolyte with an onset potential of ~0.9 V, a half-wave potential (E ½) of 0.71 V, and a selectivity for four-electron reduction of >95%. Finally and further, durability testing showed E ½ retention >95% in N 2- and O 2-saturated solutions after 2000 cycles, demonstrating the highest ORR activity and stability reported to date for GN-based electrocatalysts in acidic media.« less

Controlling the electronic structure of graphene using surface-adsorbate interactions

DOE PAGES

Matyba, Piotr; Carr, Adra; Chen, Cong; ...

2015-07-15

Hybridization of atomic orbitals in graphene on Ni(111) opens up a large energy gap of ≈2.8eV between nonhybridized states at the K point. Here we use alkali-metal adsorbate to reduce and even eliminate this energy gap, and also identify a new mechanism responsible for decoupling graphene from the Ni substrate without intercalation of atomic species underneath. Using angle-resolved photoemission spectroscopy and density functional theory calculations, we show that the energy gap is reduced to 1.3 eV due to moderate decoupling after adsorption of Na on top of graphene. Calculations confirm that after adsorption of Na, graphene bonding to Ni ismore » much weaker due to a reduced overlap of atomic orbitals, which results from n doping of graphene. Finally, we show that the energy gap is eliminated by strong decoupling resulting in a quasifreestanding graphene, which is achieved by subsequent intercalation of the Na underneath graphene. Furthermore, the ability to partially decouple graphene from a Ni substrate via n doping, with or without intercalation, suggests that the graphene-to-substrate interaction could be controlled dynamically.« less

Stacking interactions and DNA intercalation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Dr. Shen; Cooper, Valentino R; Thonhauser, Prof. Timo

2009-01-01

The relationship between stacking interactions and the intercalation of proflavine and ellipticine within DNA is investigated using a nonempirical van der Waals density functional for the correlation energy. Our results, employing a binary stack model, highlight fundamental, qualitative differences between base-pair base-pair interactions and that of the stacked intercalator base pair system. Most notable result is the paucity of torque which so distinctively defines the Twist of DNA. Surprisingly, this model, when combined with a constraint on the twist of the surrounding base-pair steps to match the observed unwinding of the sugar-phosphate backbone, was sufficient for explaining the experimentally observedmore » proflavine intercalator configuration. Our extensive mapping of the potential energy surface of base-pair intercalator interactions can provide valuable information for future nonempirical studies of DNA intercalation dynamics.« less

Metal intercalation-induced selective adatom mass transport on graphene

DOE PAGES

Liu, Xiaojie; Wang, Cai -Zhuang; Hupalo, Myron; ...

2016-03-29

Recent experiments indicate that metal intercalation is a very effective method to manipulate the graphene-adatom interaction and control metal nanostructure formation on graphene. A key question is mass transport, i.e., how atoms deposited uniformly on graphene populate different areas depending on the local intercalation. Using first-principles calculations, we show that partially intercalated graphene, with a mixture of intercalated and pristine areas, can induce an alternating electric field because of the spatial variations in electron doping, and thus, an oscillatory electrostatic potential. As a result, this alternating field can change normal stochastic adatom diffusion to biased diffusion, leading to selective massmore » transport and consequent nucleation, on either the intercalated or pristine areas, depending on the charge state of the adatoms.« less

Cobalt intercalation at the graphene/iridium(111) interface: Influence of rotational domains, wrinkles, and atomic steps

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vlaic, S.; Kimouche, A.; Coraux, J.

Using low-energy electron microscopy, we study Co intercalation under graphene grown on Ir(111). Depending on the rotational domain of graphene on which it is deposited, Co is found intercalated at different locations. While intercalated Co is observed preferentially at the substrate step edges below certain rotational domains, it is mostly found close to wrinkles below other domains. These results indicate that curved regions (near substrate atomic steps and wrinkles) of the graphene sheet facilitate Co intercalation and suggest that the strength of the graphene/Ir interaction determines which pathway is energetically more favorable.

Intercalated degrees, learning styles, and career preferences: prospective longitudinal study of UK medical students

PubMed Central

McManus, I C; Richards, P; Winder, B C

1999-01-01

Objectives To assess the effects of taking an intercalated degree (BSc) on the study habits and learning styles of medical students and on their interest in a career in medical research. Design Longitudinal questionnaire study of medical students at application to medical school and in their final year. Setting All UK medical schools. Participants 6901 medical school applicants for admission in 1991 were studied in the autumn of 1990. 3333 entered medical school in 1991 or 1992, and 2695 who were due to qualify in 1996 or 1997 were studied 3 months before the end of their clinical course. Response rates were 92% for applicants and 56% for final year students. Main outcome measures Study habits (surface, deep, and strategic learning style) and interest in different medical careers, including medical research. Identical questions were used at time of application and in final year. Results Students who had taken an intercalated degree had higher deep and strategic learning scores than at application to medical school. Those with highest degree classes had higher strategic and deep learning scores and lower surface learning scores. Students taking intercalated degrees showed greater interest in careers in medical research and laboratory medicine and less interest in general practice than their peers. The effects of the course on interest in medical research and learning styles were independent. The effect of the intercalated degree was greatest in schools where relatively few students took intercalated degrees. Conclusions Intercalated degrees result in a greater interest in research careers and higher deep and strategic learning scores. However, the effects are much reduced in schools where most students intercalate a degree. Introduction of intercalated degrees for all medical students without sufficient resources may not therefore achieve its expected effects. Key messagesAlthough intercalated degrees are well established, little is known about their effect on medical studentsIn this longitudinal study final year students who had taken intercalated degree were more interested in medical research, and had higher deep and strategic learning style scores than other studentsThe effects of the intercalated degree were dose dependent, being greatest in those gaining a first class degreeThe effects of the intercalated degree were greatest in medical schools where a relatively small proportion of medical students took the degree.Differences between medical schools are most easily explained by resource dilution PMID:10463892

Intercalation studies of zinc hydroxide chloride: Ammonia and amino acids

NASA Astrophysics Data System (ADS)

Arízaga, Gregorio Guadalupe Carbajal

2012-01-01

Zinc hydroxide chloride (ZHC) is a layered hydroxide salt with formula Zn5(OH)8Cl2·2H2O. It was tested as intercalation matrix for the first time and results were compared with intercalation products of the well-known zinc hydroxide nitrate and a Zn/Al layered double hydroxide. Ammonia was intercalated into ZHC, while no significant intercalation occurred in ZHN. Aspartic acid intercalation was only achieved by co-precipitation at pH=10 with ZHC and pH=8 with zinc hydroxide nitrate. Higher pH resistance in ZHC favored total deprotonation of both carboxylic groups of the Asp molecule. ZHC conferred more thermal protection against Asp combustion presenting exothermic peaks even at 452 °C while the exothermic event in ZHN was 366 °C and in the LDH at 276 °C.

Ethidium and proflavine binding to a 2',5'-linked RNA duplex.

PubMed

Horowitz, Eric D; Hud, Nicholas V

2006-12-06

Despite over 40 years of physical investigations, fundamental questions persist regarding the energetics of RNA and DNA intercalation. The dramatic unwinding of a nucleic acid duplex upon intercalation immediately suggests that the nucleic acid backbone should play a significant role in dictating the free energy of intercalation. However, the contribution of the backbone to intercalation free energy is difficult to appreciate given the intertwined energetics associated with intercalation (e.g., pi-pi stacking and solvent effects). Fluorescence titrations were used to determine the association constants of two known intercalators, proflavine and ethidium, for duplex 2',5'-linked RNA. Proflavine was found to bind 2',5' RNA with an association constant 25-fold greater than that measured for standard, 3',5'-linked RNA. In contrast, ethidium binds 2',5' RNA less favorably than standard RNA.

Hierarchical Porous Intercalation-Type V2 O3 as High-Performance Anode Materials for Li-Ion Batteries.

PubMed

Liu, Pengcheng; Zhu, Kongjun; Xu, Yuan; Bian, Kan; Wang, Jing; Tai, Guo'an; Gao, Yanfeng; Luo, Hongjie; Lu, Li; Liu, Jinsong

2017-06-01

As intercalation-type anode materials for Li-ion batteries (LIBs), the commercially used graphite and Li 4 Ti 5 O 12 exhibit good cycling and rate properties, but their theoretical specific capacities are too low to meet the ever-growing demands of high-energy applications such as electric vehicles. Therefore, the development of new intercalation-type anode materials with larger capacity is very desirable. Herein, we design and synthesize novel 3 D hierarchical porous V 2 O 3 @C micro/nanostructures consisting of crumpled nanosheets, through self-reduction under annealing from the structurally similar VO 2 (B)@C precursors without the addition of any other reducing reagent or gas. Excitingly, it is found for the first time through ex situ XRD technology that V 2 O 3 is a new, promising intercalation-type anode material for LIBs with a high capacity. V 2 O 3 @C micro/nanostructures can deliver a large capacity of 732 mAh g -1 without capacity loss at 100 mA g -1 even after 136 cycles, as well as exhibiting excellent cycling and rate performances. The application of V 2 O 3 for Na-ion batteries (NIBs) is elaborated for the first time, and excitingly, it is found that V 2 O 3 @C micro/nanostructures may be promising anode materials for NIBs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Purification and preparation of graphite oxide from natural graphite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Panatarani, C., E-mail: c.panatarani@phys.unpad.ac.id; Muthahhari, N.; Joni, I. Made

2016-03-11

Graphite oxide has attracted much interest as a possible route for preparation of natural graphite in the large-scale production and manipulation of graphene as a material with extraordinary electronic properties. Graphite oxide was prepared by modified Hummers method from purified natural graphite sample from West Kalimantan. We demonstrated that natural graphite is well-purified by acid leaching method. The purified graphite was proceed for intercalating process by modifying Hummers method. The modification is on the reaction time and temperature of the intercalation process. The materials used in the intercalating process are H{sub 2}SO{sub 4} and KMNO{sub 4}. The purified natural graphitemore » is analyzed by carbon content based on Loss on Ignition test. The thermo gravimetricanalysis and the Fouriertransform infrared spectroscopy are performed to investigate the oxidation results of the obtained GO which is indicated by the existence of functional groups. In addition, the X-ray diffraction and energy dispersive X-ray spectroscopy are also applied to characterize respectively for the crystal structure and elemental analysis. The results confirmed that natural graphite samples with 68% carbon content was purified into 97.68 % carbon content. While the intercalation process formed a formation of functional groups in the obtained GO. The results show that the temperature and reaction times have improved the efficiency of the oxidation process. It is concluded that these method could be considered as an important route for large-scale production of graphene.« less

Observation of Image Potential State in Oxygen Intercalated Graphene on Iridium by Two-Photon-Photoemission Spectroscopy

NASA Astrophysics Data System (ADS)

Lin, Yi; Li, Yunzhe; Sadowski, Jerzy; Dadap, Jerry; Jin, Wencan; Osgood, Richard

In this talk, we report our experimental results on the first direct observation of image potential state (IPS) in oxygen-intercalated graphene on iridium by two-photo-photoemission spectroscopy. We demonstrate how oxygen intercalation influences the IPS in Gr/Ir and decouples the interlayer interaction. We present measurements of the electronic dispersion and work function in pristine Gr/Ir, oxygen-intercalated Gr/O/Ir, and deintercalated Gr/Ir. LEED patterns are measured during the pristine, oxygen-intercalated, and deintercalated phases of the Gr/Ir sample. Based on these measurements, relative to the pristine case, the work function and the energy location of n =1 IPS relative to the Fermi level increases by 0.39 eV and 0.3 eV, respectively, due to oxygen intercalation, whereas the effective mass of n =1 IPS is hardly influenced by the intercalation process. Moreover, we achieve the quenching and restoration of the resonance from Ir Rashba states to n =1 IPS in Gr/Ir by oxygen intercalation and deintercalation. This work was supported by the DOE, Office of Basic Energy Sciences, Division of MSE under Contract No. DE-FG 02-04-ER-46157. This research used resources of the CFN, which is the U.S. DOE Office of Science User Facility, under Contract No. DE-SC0012704.

De nouveaux éléments structuraux du complexe aquifère profond du bassin du Rharb (Maroc) : implications hydrogéologiques

NASA Astrophysics Data System (ADS)

Kili, Malika; El Mansouri, Bouabid; Chao, Jamal; Fora, Abderrahman Ait

2006-12-01

The Rharb basin is located in northwestern Morocco. It is a part of one of the most important hydrogeological basins of Morocco, and extends over some 4000 km 2. The nature of its Plio-Quaternary sedimentary fill and its structural and palaeoenvironmental contexts are reflected by great variations in aerial and temporal facies distribution. This distribution, in turn, is a direct cause of the observed complexity in the geometry of potentially water-bearing beds. In the present work, we present an image of potential new hydrogeological reservoirs and define new structures that partially explain their architecture. To cite this article: M. Kili et al., C. R. Geoscience 338 (2006).

La cosmologie de Kant dans l'Histoire générale de la Nature et théorie du ciel (1755).

NASA Astrophysics Data System (ADS)

Seidengart, J.

In his scientifical works Newton was not in position to solve the cosmological problems without calling on the help of God's Providence: for instance, the structure of the universe, its stability, the problem of its origin, of its process of formation, of its evolution. For the first time in the history of astronomy, Kant's Universal Natural History and Theory of the Heavens (1755) conceived correctly the structure of our Galaxy, and then developped the famous theory of "Island Universes". In the second part of this article the author gives a survey of the nebular hypothesis developped by Kant 40 years before Laplace's Exposition du système du Monde.

Bio-Based Nano Composites from Plant Oil and Nano Clay

NASA Astrophysics Data System (ADS)

Lu, Jue; Hong, Chang K.; Wool, Richard P.

2003-03-01

We explored the combination of nanoclay with new chemically functionalized, amphiphilic, plant oil resins to form bio-based nanocomposites with improved physical and mechanical properties. These can be used in many new applications, including the development of self-healing nanocomposites through controlled reversible exfoliation/intercalation, and self-assembled nano-structures. Several chemically modified triglyceride monomers of varying polarity, combined with styrene (ca 30include acrylated epoxidized soybean oil (AESO), maleated acrylated epoxidized soybean oil (MAESO) and soybean oil pentaerythritol glyceride maleates (SOPERMA), containing either hydroxyl group or acid functionality or both. The clay used is a natural montmorillonite modified with methyl tallow bis-2-hydroxyethyl quaternary ammonium chloride, which has hydroxyl groups. Both XRD and TEM showed a completely exfoliated structure at 3 wtwhen the clay content is above 5 wtconsidered a mix of intercalated and partially exfoliated structure. The controlled polarity of the monomer has a major effect on the reversible dispersion of clay in the polymer matrix. The bio-based nanocomposites showed a significant increase in flexural modulus and strength. Supported by EPA and DoE

Torsional mechanics of DNA are regulated by small-molecule intercalation.

PubMed

Celedon, Alfredo; Wirtz, Denis; Sun, Sean

2010-12-23

Whether the bend and twist mechanics of DNA molecules are coupled is unclear. Here, we report the direct measurement of the resistive torque of single DNA molecules to study the effect of ethidium bromide (EtBr) intercalation and pulling force on DNA twist mechanics. DNA molecules were overwound and unwound using recently developed magnetic tweezers where the molecular resistive torque was obtained from Brownian angular fluctuations. The effect of EtBr intercalation on the twist stiffness was found to be significantly different from the effect on the bend persistence length. The twist stiffness of DNA was dramatically reduced at low intercalator concentration (<10 nM); however, it did not decrease further when the intercalator concentration was increased by 3 orders of magnitude. We also determined the dependence of EtBr intercalation on the torque applied to DNA. We propose a model for the elasticity of DNA base pairs with intercalated EtBr molecules to explain the abrupt decrease of twist stiffness at low EtBr concentration. These results indicate that the bend and twist stiffnesses of DNA are independent and can be differently affected by small-molecule binding.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed Central

2013-01-01

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

Synergetic effects of K + and Mg 2+ ion intercalation on the electrochemical and actuation properties of the two-dimensional Ti 3 C 2 MXene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Qiang; Come, Jeremy; Naguib, Michael

2017-01-01

Two-dimensional materials, such as MXenes, are attractive candidates for energy storage and electrochemical actuators due to their high volume changes upon ion intercalation. Of special interest for boosting energy storage is the intercalation of multivalent ions such as Mg 2+, which suffers from sluggish intercalation and transport kinetics due to its ion size. By combining traditional electrochemical characterization techniques with electrochemical dilatometry and contact resonance atomic force microscopy, the synergetic effects of the pre-intercalation of K +ions are demonstrated to improve the charge storage of multivalent ions, as well as tune the mechanical and actuation properties of the Ti 3Cmore » 2MXene. Our results have important implications for quantitatively understanding the charge storage processes in intercalation compounds and provide a new path for studying the mechanical evolution of energy storage materials.« less

Constraint on the potassium content for the superconductivity of potassium-intercalated phenanthrene.

PubMed

Huang, Qiao-Wei; Zhong, Guo-Hua; Zhang, Jiang; Zhao, Xiao-Miao; Zhang, Chao; Lin, Hai-Qing; Chen, Xiao-Jia

2014-03-21

Raman-scattering measurements were performed on K(x)phenanthrene (0 ⩽ x ⩽ 6.0) at room temperature. Three phases (x = 3.0, 3.5, and 4.0) are identified based on the obtained Raman spectra. Only the K3phenanthrene phase is found to exhibit the superconducting transition at 5 K. The C-C stretching modes are observed to broaden and become disordered in K(x)phenanthrene with x = 2.0, 2.5, 6.0, indicating some molecular disorder in the metal intercalation process. This disorder is expected to influence the nonmetallic nature of these materials. The absence of metallic character in these nonsuperconducting phases is found from the calculated electronic structures based on the local density approximation.

Structure-function correlation of chloroquine and analogues as transgene expression enhancers in nonviral gene delivery.

PubMed

Cheng, Jianjun; Zeidan, Ryan; Mishra, Swaroop; Liu, Aijie; Pun, Suzie H; Kulkarni, Rajan P; Jensen, Gregory S; Bellocq, Nathalie C; Davis, Mark E

2006-11-02

To understand how chloroquine (CQ) enhances transgene expression in polycation-based, nonviral gene delivery systems, a number of CQ analogues with variations in the aliphatic amino side chain or in the aromatic ring are synthesized and investigated. Our studies indicate that the aliphatic amino moiety of CQ is essential to provide increased gene expression. Further, the enhancements are more dramatically affected by changes to the aromatic ring and are positively correlated to the strength of intercalation between DNA and the CQ analogues. Quinacrine (QC), a CQ analogue with a fused acridinyl structure that can strongly intercalate DNA, enhances transfection similarly to CQ at a concentration 10 times lower, while N(4)-(4-pyridinyl)-N(1),N(1)-diethyl-1,4-pentanediamine (CP), a CQ analogue that has a weakly intercalating pyridinyl ring, shows no effect on gene expression. Subtle change on the 7-substituent of the chloroquine aromatic structure can also greatly affect the ability of the CQ analogues to enhance transgene expression. Transfection in the presence of N(4)-(7-trifluoromethyl-4-quinolinyl)-N(1),N(1)-diethyl-1,4-pentanediamin e (CQ7a) shows expression efficiency 10 times higher than in the presence of CQ at same concentration, while transfection in the presence of N(4)-(4-quinolinyl)-N(1),N(1)-diethyl-1,4-pentanediamine (CQ7b) does not reveal any enhancing effects on expression. Through a number of comparative studies with CQ and its analogues, we conclude that there are at least three mechanistic features of CQ that lead to the enhancement in gene expression: (i) pH buffering in endocytic vesicles, (ii) displacement of polycations from the nucleic acids in polyplexes, and (iii) alteration of the biophysical properties of the released nucleic acid.

Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries

DOE PAGES

Byles, B. W.; West, P.; Cullen, D. A.; ...

2015-12-03

Extended hydrothermal treatment at an elevated temperature of 220 °C allowed high yield synthesis of manganese oxide nanowires with a todorokite crystal structure suitable for ions intercalation. The flexible, high aspect ratio nanowires are 50–100 nm in diameter and up to several microns long, with 3 × 3 structural tunnels running parallel to the nanowire longitudinal axis. Moreover, the tunnels are occupied by magnesium ions and water molecules, with the chemical composition found to be Mg 0.2MnO 2·0.5H 2O. The todorokite nanowires were, for the first time, electrochemically tested in both Li-ion and Na-ion cells. A first discharge capacity ofmore » 158 mA h g -1 was achieved in a Na-ion system, which was found to be greater than the first discharge capacity in a Li-ion system (133 mA h g -1). In spite of the large structural tunnel dimensions, todorokite showed a significant first cycle capacity loss in a Na-ion battery. After 20 cycles, the capacity was found to stabilize around 50 mA h g -1 and remained at this level for 100 cycles. In a Li-ion system, todorokite nanowires showed significantly better capacity retention with 78% of its initial capacity remaining after 100 cycles. Rate capability tests also showed superior performance of todorokite nanowires in Li-ion cells compared to Na-ion cells at higher current rates. Finally, these results highlight the difference in electrochemical cycling behavior of Li-ion and Na-ion batteries for a host material with spacious 3 × 3 tunnels tailored for large Na + ion intercalation.« less

Chronic hemodynamic overload of the atria is an important factor for gap junction remodeling in human and rat hearts.

PubMed

Rucker-Martin, Catherine; Milliez, Paul; Tan, Sisareuth; Decrouy, Xavier; Recouvreur, Michel; Vranckx, Roger; Delcayre, Claude; Renaud, Jean-François; Dunia, Irene; Segretain, Dominique; Hatem, Stéphane N

2006-10-01

The expression and distribution of connexins is abnormal in a number of cardiac diseases, including atrial fibrillation, and is believed to favor conduction slowing and arrhythmia. Here, we studied the role of atrial structural remodeling in the disorganization of gap junctions and whether redistributed connexins can form new functional junction channels. Expression of connexin-43 (Cx43) was characterized by immunoblotting and immunohistochemistry in human right atrial specimens and in rat atria after myocardial infarction (MI). Gap junctions were studied by electron and 3-D microscopy, and myocyte-myocyte coupling was determined by Lucifer yellow dye transfer. In both chronically hemodynamically overloaded human atria in sinus rhythm and in dilated atria from MI-rats, Cx43 were dephosphorylated and redistributed from the intercalated disc to the lateral cell membranes as observed during atrial fibrillation. In MI-rats, the gap junctions at the intercalated disc were smaller (20% decrease) and contained very little Cx43 (0 or 1 gold particle vs. 42 to 98 in sham-operated rats). In the lateral membranes of myocytes, numerous connexon aggregates comprising non-phosphorylated Cx43 were observed. These connexon aggregates were in no case assembled into gap junction plaque-like structures. However, N-cadherin was well organized in the intercalated disc. There was very little myocyte-myocyte coupling in MI-rat atria and no myocyte-fibroblast coupling. Regression of the atrial remodeling was associated with the normalization of Cx43 localization. Structural alteration of the atrial myocardium is an important factor in the disorganization of connexins and gap junction. Moreover, redistributed Cx43 do not form junction channels.

Ecological risk assessment of depleted uranium in the environment at Aberdeen Proving Ground

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clements, W.H.; Kennedy, P.L.; Myers, O.B.

1993-01-01

A preliminary ecological risk assessment was conducted to evaluate the effects of depleted uranium (DU) in the Aberdeen Proving Ground (APG) ecosystem and its potential for human health effects. An ecological risk assessment of DU should include the processes of hazard identification, dose-response assessment, exposure assessment, and risk characterization. Ecological risk assessments also should explicitly examine risks incurred by nonhuman as well as human populations, because risk assessments based only on human health do not always protect other species. To begin to assess the potential ecological risk of DU release to the environment we modeled DU transport through the principalmore » components of the aquatic ecosystem at APG. We focused on the APG aquatic system because of the close proximity of the Chesapeake Bay and concerns about potential impacts on this ecosystem. Our objective in using a model to estimate environmental fate of DU is to ultimately reduce the uncertainty about predicted ecological risks due to DU from APG. The model functions to summarize information on the structure and functional properties of the APG aquatic system, to provide an exposure assessment by estimating the fate of DU in the environment, and to evaluate the sources of uncertainty about DU transport.« less

Ecological risk assessment of depleted uranium in the environment at Aberdeen Proving Ground. Annual report, 1991

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clements, W.H.; Kennedy, P.L.; Myers, O.B.

1993-03-01

A preliminary ecological risk assessment was conducted to evaluate the effects of depleted uranium (DU) in the Aberdeen Proving Ground (APG) ecosystem and its potential for human health effects. An ecological risk assessment of DU should include the processes of hazard identification, dose-response assessment, exposure assessment, and risk characterization. Ecological risk assessments also should explicitly examine risks incurred by nonhuman as well as human populations, because risk assessments based only on human health do not always protect other species. To begin to assess the potential ecological risk of DU release to the environment we modeled DU transport through the principalmore » components of the aquatic ecosystem at APG. We focused on the APG aquatic system because of the close proximity of the Chesapeake Bay and concerns about potential impacts on this ecosystem. Our objective in using a model to estimate environmental fate of DU is to ultimately reduce the uncertainty about predicted ecological risks due to DU from APG. The model functions to summarize information on the structure and functional properties of the APG aquatic system, to provide an exposure assessment by estimating the fate of DU in the environment, and to evaluate the sources of uncertainty about DU transport.« less

Design of Perovskite Oxides as Anion-Intercalation-Type Electrodes for Supercapacitors: Cation Leaching Effect.

PubMed

Liu, Yu; Dinh, Jim; Tade, Moses O; Shao, Zongping

2016-09-14

Oxygen ions can be exploited as a charge carrier to effectively realize a new type of anion-intercalation supercapacitor. In this study, to get some useful guidelines for future materials development, we comparatively studied SrCoO3-δ (SC), Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), and Co3O4 as electrodes in supercapacitors with aqueous alkaline electrolyte. The effect of interaction between the electrode materials with the alkaline solution was focused on the structure and specific surface area of the electrode material, and ultimately the electrochemical performance was emphasized. Both BSCF and SC were found to experience cation leaching in alkaline solution, resulting in an increase in the specific surface area of the material, but overleaching caused the damage of perovskite structure of BSCF. Barium leaching was more serious than strontium, and the cation leaching was component dependent. Although high initial capacitance was achieved for BSCF, it was not a good candidate as intercalation-type electrode for supercapacitor because of poor cycling stability from serious Ba(2+) and Sr(2+) leaching. Instead, SC was a favorable electrode candidate for practical use in supercapacitors due to its high capacity and proper cation leaching capacity, which brought beneficial effect on cycling stability. It is suggested that cation leaching effect should be seriously considered in the development of new perovskite materials as electrodes for supercapacitors.

Moderate temperature rechargeable sodium batteries

NASA Technical Reports Server (NTRS)

Abraham, K. M.; Rupich, M. W.; Pitts, L.; Elliott, J. E.

1983-01-01

Cells utilizing the organic electrolyte, NaI in triglyme, operated at approx. 130 C with Na(+) - intercalating cathodes. However, their rate and stability were inadequate. NaAlCl4 was found to be a highly useful electrolyte for cell operation at 165-190 C. Na(+) intercalating chalcogenides reacted with NaAlCl4 during cycling to form stable phases. Thus, VS2 became essentially VS2Cl, with reversible capacity of approx 2.8 e(-)/V, and a mid-discharge voltage of approx 2.5V and 100 deep discharge cycles were readily achieved. A positive electrode consisting of VCl3 and S plus NaAlCl4 was subjected to deep-discharge cycles 300 times and it demonstrated identity with the in-situ-formed BSxCly cathode. NiS2 and NiS which are not Na(+)-intercalating structures formed highly reversible electrodes in NaAlCl4. The indicated discharge mechanism implies a theoretical capacity 4e(-)/Ni for NiS2 and 2e(-)/Ni for NiS. The mid-discharge potentials are, respectively, 2.4V and 2.1V. A Na/NiS2 cell cycling at a C/5 rate has exceeded 500 deep discharge cycles with 2.5e(-)/Ni average utilization. A 4 A-hr nominal capacity prototype Na/NiS2 cell was tested at 190 C. It was voluntarily terminated after 80 cycles. Further development, particularly of cathode structure and hardware should produce a battery capable of at least 50-W-hr/lb and more than 1000 cycles.

Hierarchical MoS2-coated three-dimensional graphene network for enhanced supercapacitor performances

NASA Astrophysics Data System (ADS)

Zhou, Rui; Han, Cheng-jie; Wang, Xiao-min

2017-06-01

Layered molybdenum disulfide (MoS2) owns graphene-like two-dimensional structure, and when used as the electrode material for energy storage devices, the intercalation of electrolyte ions is permitted. Herein, a simple dipping and drying method is employed to stack few-layered MoS2 nanosheets on a three-dimensional graphene network (3DGN). The structure measurement results indicate that the assembled hierarchical MoS2 nanosheets own expanded interlayer spacing (∼0.75 nm) and are stacked on the surface of 3DGN uncontinuously. The composite can achieve 110.57% capacitance retention after 4000 cycles of galvanostatic charge/discharge tests and 76.73% capacitance retention with increasing the current density from 1 A g-1 to 100 A g-1. Moreover, the asymmetric coin cell supercapacitor using MoS2@3DGN and active carbon as electrode materials is assembled. This device could achieve a working voltage window of 1.6 V along with the power and energy densities of 400.0-8001.6 W kg-1 and 36.43-1.12 Wh kg-1 respectively. The enhanced electrochemical performance can be attributed to: (1) the expanded interlayer spacing of hierarchical MoS2 nanosheets which can facilitate the fast intercalation/deintercalation of electrolyte cations, (2) the uncontinuous deposition of hierarchical MoS2 nanosheets which facilitates more contact between electrolyte and the section of MoS2 nanosheets to provide more gates for the intercalation/deintercalation.

Probing the DNA kink structure induced by the hyperthermophilic chromosomal protein Sac7d

PubMed Central

Chen, Chin-Yu; Ko, Tzu-Ping; Lin, Ting-Wan; Chou, Chia-Cheng; Chen, Chun-Jung; Wang, Andrew H.-J.

2005-01-01

Sac7d, a small, abundant, sequence-general DNA-binding protein from the hyperthermophilic archaeon Sulfolobus acidocaldarius, causes a single-step sharp kink in DNA (∼60°) via the intercalation of both Val26 and Met29. These two amino acids were systematically changed in size to probe their effects on DNA kinking. Eight crystal structures of five Sac7d mutant–DNA complexes have been analyzed. The DNA-binding pattern of the V26A and M29A single mutants is similar to that of the wild-type, whereas the V26A/M29A protein binds DNA without side chain intercalation, resulting in a smaller overall bending (∼50°). The M29F mutant inserts the Phe29 side chain orthogonally to the C2pG3 step without stacking with base pairs, inducing a sharp kink (∼80°). In the V26F/M29F-GCGATCGC complex, Phe26 intercalates deeply into DNA bases by stacking with the G3 base, whereas Phe29 is stacked on the G15 deoxyribose, in a way similar to those used by the TATA box-binding proteins. All mutants have reduced DNA-stabilizing ability, as indicated by their lower Tm values. The DNA kink patterns caused by different combinations of hydrophobic side chains may be relevant in understanding the manner by which other minor groove-binding proteins interact with DNA. PMID:15653643

Electrical and galvanomagnetic properties of nanoporous carbon samples impregnated with bromine

NASA Astrophysics Data System (ADS)

Danishevskii, A. M.; Popov, V. V.; Kyutt, R. N.; Gordeev, S. K.

2013-07-01

Nanoporous carbon samples with a large specific surface area can be filled with heavier elements or their compounds, which makes it possible to investigate the interaction of their electronic subsystems with carbon. One of the elements convenient for filling pores of carbon materials is bromine. Impregnation of nanoporous carbon samples with bromine causes the occurrence of the processes of micropore filling, monolayer adsorption, and intercalation. It has been found that samples impregnated with bromine substantially change their electrical and galvanomagnetic properties, and these changes depend on the structure of the samples. It has been shown that, if in the skeleton of a porous carbon sample there is a fraction of graphite clusters, the impregnation of the sample with bromine increases the concentration of charged carriers (holes). But when the sample has a quasi-amorphous structure, the injection of bromine into the sample leads to the appearance of a certain concentration of electrons in addition to charged mobile holes of the initial sample; i.e., the electrical conductivity becomes bipolar. In the former case, bromine molecules intercalate graphite clusters and, since bromine is an acceptor during intercalation of graphite, the hole concentration in the carbon skeleton network increases. In the latter case, bromine molecules can only be adsorbed on pore walls. As a result, the adsorption interaction between the electron shells of bromine molecules and the carbon surface leads to the formation of a donor layer near the surface and to the generation of electrons in the carbon skeleton network.

Synthesis of a drug delivery vehicle for cancer treatment utilizing DNA-functionalized gold nanoparticles

NASA Astrophysics Data System (ADS)

Brann, Tyler

The treatment of cancer with chemotherapeutic agents has made great strides in the last few decades but still introduces major systemic side effects. The potent drugs needed to kill cancer cells often cause irreparable damage to otherwise healthy organs leading to further morbidity and mortality. A therapy with intrinsic selective properties and/or an inducible activation has the potential to change the way cancer can be treated. Gold nanoparticles (GNPs) are biocompatible and chemically versatile tools that can be readily functionalized to serve as molecular vehicles. The ability of these particles to strongly absorb light with wavelengths in the therapeutic window combined with the heating effect of surface plasmon resonance makes them uniquely suited for noninvasive heating in biologic applications. Specially designed DNA aptamers have shown their ability to serve as drug carriers through intercalation as well as directly acting as therapeutic agents. By combining these separate molecules a multifaceted drug delivery vehicle can be created with great potential as a selective and controllable treatment for cancer. Oligonucleotide-coated GNPs have been created using spherical GNPs but little work has been reported using gold nanoplates in this way. Using the Diasynth method gold nanoplates were produced to absorb strongly in the therapeutic near infrared (nIR) window. These particles were functionalized with two DNA oligonucleotides: one serving as an intercalation site for doxorubicin, and another, AS1411, serving directly as an anticancer targeting/therapeutic agent. These functional particles were fully synthesized and processed along with confirmation of DNA functionalization and doxorubicin intercalation. Doxorubicin is released via denaturation of the DNA structure into which doxorubicin is intercalated upon the heating of the gold nanoplate well above the DNA melting temperature. This temperature increase, due to light stimulation of surface plasmon resonance, was measured during laser application. Successful release of doxorubicin via laser application was measured with fluorescence measurements providing proof that the doxorubicin was successfully intercalated and released.

Alkali metal intercalates of molybdenum disulfide.

NASA Technical Reports Server (NTRS)

Somoano, R. B.; Hadek, V.; Rembaum, A.

1973-01-01

Study of some of the physicochemical properties of compounds obtained by subjecting natural molybdenite and single crystals of molybdenum disulfide grown by chemical vapor transport to intercalation with the alkali group of metals (Li, Na, K, Rb, and Cs) by means of the liquid ammonia technique. Reported data and results include: (1) the intercalation of the entire alkali metal group, (2) stoichiometries and X-ray data on all of the compounds, and (3) superconductivity data for all the intercalation compounds.

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

PubMed Central

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

First-principles theory of cation and intercalation ordering in Li xCoO 2

NASA Astrophysics Data System (ADS)

Wolverton, C.; Zunger, Alex

Several types of cation- and vacancy-ordering are of interest in the Li xCoO 2 battery cathode material since they can have a profound effect on the battery voltage. We present a first-principles theoretical approach which can be used to calculate both cation- and vacancy-ordering patterns at both zero and finite temperatures. This theory also provides quantum-mechanical predictions (i.e., without the use of any experimental input) of battery voltages of both ordered and disordered Li xCoO 2/Li cells from the energetics of the Li intercalation reactions. Our calculations allow us to search the entire configurational space to predict the lowest-energy ground-state structures, search for large voltage cathodes, explore metastable low-energy states, and extend our calculations to finite temperatures, thereby searching for order-disorder transitions and states of partial disorder. We present the first prediction of the stable spinel structure LiCo 2O 4 for the 50% delithiated Li 0.5CoO 2.

Superconductivity at 7.4 K in few layer graphene by Li-intercalation.

PubMed

Tiwari, Anand P; Shin, Soohyeon; Hwang, Eunhee; Jung, Soon-Gil; Park, Tuson; Lee, Hyoyoung

2017-11-08

Superconductivity in graphene has been highly sought after for its promise in various device applications and for general scientific interest. Ironically, the simple electronic structure of graphene, which is responsible for novel quantum phenomena, hinders the emergence of superconductivity. Theory predicts that doping the surface of the graphene effectively alters the electronic structure, thus promoting propensity towards Cooper pair instability (Profeta et al (2012) Nat. Phys. 8 131-4; Nandkishore et al (2012) Nat. Phys. 8 158-63) [1, 2]. Here we report the emergence of superconductivity at 7.4 K in Li-intercalated few-layer-graphene (FLG). The absence of superconductivity in 3D Li-doped graphite underlines that superconductivity in Li-FLG arises from the novel electronic properties of the 2D graphene layer. These results are expected to guide future research on graphene-based superconductivity, both in theory and experiments. In addition, easy control of the Li-doping process holds promise for various device applications.

Alkali metal intercalated fullerene-like MS(2) (M = W, Mo) nanoparticles and their properties.

PubMed

Zak, Alla; Feldman, Yishay; Lyakhovitskaya, Vera; Leitus, Gregory; Popovitz-Biro, Ronit; Wachtel, Ellen; Cohen, Hagai; Reich, Shimon; Tenne, Reshef

2002-05-01

Layered metal disulfides-MS(2) (M = Mo, W) in the form of fullerene-like nanoparticles and in the form of platelets (crystallites of the 2H polytype) have been intercalated by exposure to alkali metal (potassium and sodium) vapor using a two-zone transport method. The composition of the intercalated systems was established using X-ray energy dispersive spectrometer and X-ray photoelectron spectroscopy (XPS). The alkali metal concentration in the host lattice was found to depend on the kind of sample and the experimental conditions. Furthermore, an inhomogeneity of the intercalated samples was observed. The product consisted of both nonintercalated and intercalated phases. X-ray diffraction analysis and transmission electron microscopy of the samples, which were not exposed to the ambient atmosphere, showed that they suffered little change in their lattice parameters. On the other hand, after exposure to ambient atmosphere, substantial increase in the interplanar spacing (3-5 A) was observed for the intercalated phases. Insertion of one to two water molecules per intercalated metal atom was suggested as a possible explanation for this large expansion along the c-axis. Deintercalation of the hydrated alkali atoms and restacking of the MS(2) layers was observed in all the samples after prolonged exposure to the atmosphere. Electric field induced deintercalation of the alkali metal atoms from the host lattice was also observed by means of the XPS technique. Magnetic moment measurements for all the samples indicate a diamagnetic to paramagnetic transition after intercalation. Measurements of the transport properties reveal a semiconductor to metal transition for the heavily K intercalated 2H-MoS(2). Other samples show several orders of magnitude decrease in resistivity and two- to five-fold decrease in activation energies upon intercalation. These modifications are believed to occur via charge transfer from the alkali metal to the conduction band of the host lattice. Recovery of the pristine compound properties (diamagnetism and semiconductivity) was observed as a result of deintercalation.

Real-time electrochemical LAMP: a rational comparative study of different DNA intercalating and non-intercalating redox probes.

PubMed

Martin, Alexandra; Bouffier, Laurent; Grant, Kathryn B; Limoges, Benoît; Marchal, Damien

2016-06-20

We present a comparative study of ten redox-active probes for use in real-time electrochemical loop-mediated isothermal amplification (LAMP). Our main objectives were to establish the criteria that need to be fulfilled for minimizing some of the current limitations of the technique and to provide future guidelines in the search for ideal redox reporters. To ensure a reliable comparative study, each redox probe was tested under similar conditions using the same LAMP reaction and the same entirely automatized custom-made real-time electrochemical device (designed for electrochemically monitoring in real-time and in parallel up to 48 LAMP samples). Electrochemical melt curve analyses were recorded immediately at the end of each LAMP reaction. Our results show that there are a number of intercalating and non-intercalating redox compounds suitable for real-time electrochemical LAMP and that the best candidates are those able to intercalate strongly into ds-DNA but not too much to avoid inhibition of the LAMP reaction. The strongest intercalating redox probes were finally shown to provide higher LAMP sensitivity, speed, greater signal amplitude, and cleaner-cut DNA melting curves than the non-intercalating molecules.

Transition metal intercalated bilayer silicene

NASA Astrophysics Data System (ADS)

Pandey, Dhanshree; Kamal, C.; Chakrabarti, Aparna

2018-04-01

We investigate the electronic and magnetic properties of Mn, Fe and Co-intercalated silicene bilayer with AA and AB stacking by using spin polarized density functional theory. The intercalation of Mn increases the gap between the two layers of silicene due to the larger atomic radii of Mn as compared to Fe and Co. Bader charge analysis has been performed to understand the bonding between the TM and Si atoms. This also helps in explaining the magnetic moment possessed by the composite systems after intercalating TM in between the layers of bilayer silicene system. This study reveals that a significant net magnetic moment is observed in cases of Mn-intercalated silicene bilayers, whereas Fe has a very small moment of 0.78 µB in the case of AA stacking configuration only. Co intercalation leads to net zero magnetic moment. Further, we find that Fe and Co marginally favor the AB stacking whereas Mn has a slight preference of the AA over the AB configuration. The composite systems, specifically when intercalated with Fe and Co atoms, favor a hybridization which is far away from sp3-like hybridization along the plane of Si atoms in bilayer silicene.

Modelling, Simulation & Analysis (MS&A): Potent Enabling Tools for Planning and Executing Complex Major National Events

DTIC Science & Technology

2011-10-01

de 2012 à Londres, les Jeux du Commonwealth de 2015 à Toronto et la gestion des cas d’urgence transfrontaliers...tels que les Jeux olympiques. La gestion de la sécurité lors d’événements comme Vancouver 2010 et les sommets du G8 et du G20 est un enjeu... des plans de gestion des mesures d’urgence et de continuité des opérations, une structure permanente a été mise sur pied

Chitosan/zinc oxide-polyvinylpyrrolidone (CS/ZnO-PVP) nanocomposite for better thermal and antibacterial activity.

PubMed

Karpuraranjith, M; Thambidurai, S

2017-11-01

A new biopolymer based ZnO-PVP nanocomposite was successfully synthesized by single step in situ precipitation method using chitosan as biosurfactant, zinc chloride as a source material, PVP as stabilizing agent and sodium hydroxide as precipitating agent. The chemical bonding and crystalline behaviors of chitosan, zinc oxide and PVP were confirmed by FT-IR and XRD analysis. The biopolymer connected ZnO particles intercalated PVP matrix was layer and rod like structure appeared in nanometer range confirmed by HR-SEM and TEM analysis. The surface topography image of CS/ZnO-PVP nanocomposite was obtained in the average thickness of 12nm was confirmed by AFM analysis. Thermal stability of cationic biopolymer based ZnO intercalated PVP has higher stability than CS-PVP and chitosan. Consequently, antimicrobial activity of chitosan/ZnO-PVP matrix acts as a better microbial inhibition activity than PVP-ZnO nanocomposite. The obtained above results demonstrate that CS and ZnO intercalated PVP matrix has better reinforced effect than other components. Therefore, Chitosan/ZnO-PVP nanocomposite may be a promising material for the biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang Lijing; Xu Xiangyu; Evans, David G.

2010-05-15

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

Exploring DNA binding and nucleolytic activity of few 4-aminoantipyrine based amino acid Schiff base complexes: A comparative approach

NASA Astrophysics Data System (ADS)

Raman, N.; Sakthivel, A.; Pravin, N.

A series of novel Co(II), Cu(II), Ni(II) and Zn(II) complexes were synthesized from Schiff base(s), obtained by the condensation of 4-aminoantipyrine with furfural and amino acid (glycine(L1)/alanine(L2)/valine(L3)) and respective metal(II) chloride. Their structural features and other properties were explored from the analytical and spectral methods. The binding behaviors of the complexes to calf thymus DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. The intrinsic binding constants for the above synthesized complexes are found to be in the order of 102 to 105 indicating that most of the synthesized complexes are good intercalators. The binding constant values (Kb) clearly indicate that valine Schiff-base complexes have more intercalating ability than alanine and glycine Schiff-base complexes. The results indicate that the complexes bind to DNA through intercalation and act as efficient cleaving agents. The in vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents against various pathogens. The IC50 values of [Ni(L1)2] and [Zn(L1)2] complexes imply that these complexes have preferable ability to scavenge hydroxyl radical.

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

PubMed

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

2003-07-28

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

Intercalation chemistry of zirconium 4-sulfophenylphosphonate

NASA Astrophysics Data System (ADS)

Svoboda, Jan; Zima, Vítězslav; Melánová, Klára; Beneš, Ludvík; Trchová, Miroslava

2013-12-01

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.

Synthesis of new oligothiophene derivatives and their intercalation compounds: Orientation effects

USGS Publications Warehouse

Ibrahim, M.A.; Lee, B.-G.; Park, N.-G.; Pugh, J.R.; Eberl, D.D.; Frank, A.J.

1999-01-01

The orientation dependence of intercalated oligothiophene derivatives in vermiculite and metal disulfides MS2 (M = Mo, Ti and Zr) on the pendant group on the thiophene ring and the host material was studied by X-ray diffraction (XRD) and solid state nuclear magnetic resonance spectroscopy. Amino and nitro derivatives of bi-, ter- and quarter-thiophenes were synthesized for the first time. The amino-oligothiophenes were intercalated into vermiculite by an exchange reaction with previously intercalated octadecylammonium vermiculite and into MS2 by the intercalation-exfoliation technique. Analysis of the XRD data indicates that a monolayer of amino-oligothiophene orients perpendicularly to the silicate surface in vermiculite and lies flat in the van der Waals gap of MS2.

Suppression of Interchannel Interference in FM Receivers

DTIC Science & Technology

1979-07-01

construed as an official Depart- ment of the Army position, unlessa so designated by other authorized docum ents. 19. KE£Y WORiZS (Centinae an toeva side...receiver structure is derived. Then, experimental results on a detector designed by copying the topology of the optimum receiver structure are...and autocorrelation Rm (T) and R (T). We designate t xl(t) = J rl(u) du (2) -t Xz(t) m n(u)du (3) This converts the FM waves s1(t) and s,(t) into

Thermodynamic and spectroscopic investigations of TMPyP4 association with guanine- and cytosine-rich DNA and RNA repeats of C9orf72.

PubMed

Alniss, Hasan; Zamiri, Bita; Khalaj, Melisa; Pearson, Christopher E; Macgregor, Robert B

2018-01-22

An expansion of the hexanucleotide repeat (GGGGCC)n·(GGCCCC)n in the C9orf72 promoter has been shown to be the cause of Amyotrophic lateral sclerosis and frontotemporal dementia (ALS-FTD). The C9orf72 repeat can form four-stranded structures; the cationic porphyrin (TMPyP4) binds and distorts these structures. Isothermal titration calorimetry (ITC), and circular dichroism (CD) were used to study the binding of TMPyP4 to the C-rich and G-rich DNA and RNA oligos containing the hexanucleotide repeat at pH 7.5 and 0.1 M K + . The CD spectra of G-rich DNA and RNA TMPyP4 complexes showed features of antiparallel and parallel G-quadruplexes, respectively. The shoulder at 260 nm in the CD spectrum becomes more intense upon formation of complexes between TMPyP4 and the C-rich DNA. The peak at 290 nm becomes more intense in the c-rich RNA molecules, suggesting induction of an i-motif structure. The ITC data showed that TMPyP4 binds at two independent sites for all DNA and RNA molecules. For DNA, the data are consistent with TMPyP4 stacking on the terminal tetrads and intercalation. For RNA, the thermodynamics of the two binding modes are consistent with groove binding and intercalation. In both cases, intercalation is the weaker binding mode. These findings are considered with respect to the structural differences of the folded DNA and RNA molecules and the energetics of the processes that drive site-specific recognition by TMPyP4; these data will be helpful in efforts to optimize the specificity and affinity of the binding of porphyrin-like molecules. Copyright © 2018 Elsevier Inc. All rights reserved.

Rechargeable LiNiO2/carbon cells

NASA Astrophysics Data System (ADS)

Dahn, J. R.; von Sacken, U.; Juzkow, M. W.; Al-Janaby, H.

1991-08-01

Rechargeable cells can be made using two different intercalation compounds, in which the chemical potential of the intercalant differs by several eV, for the electrodes. The factors that play a role in the selection of appropriate lithium intercalation compounds for such cells are discussed. For the ease of cell assembly, the cathode should be stable in air when it is fully intercalated, like LiNiO2. For the anode, the chemical potential of the intercalated Li should be close to that of Li metal, like it is in Li(x)C6. The intercalation of Li in LiNiO2 is discussed, and then in petroleum coke. Then, it is shown that LiNiO2/coke cells have high energy density, long cycle life, excellent high-temperature performance, low self-discharge rates, can be repeatedly discharged to zero volts without damage, and are easily fabricated. It is considered that this type of cell shows far more promise for widespread applications than traditional secondary Li cells using metallic Li anodes.

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition

PubMed Central

Nakayama, Hirokazu; Hayashi, Aki

2014-01-01

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids. PMID:25080007

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition.

PubMed

Nakayama, Hirokazu; Hayashi, Aki

2014-07-30

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids.

New X-ray insight into oxygen intercalation in epitaxial graphene grown on 4H-SiC(0001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kowalski, G., E-mail: kowal@fuw.edu.pl; Tokarczyk, M.; Dąbrowski, P.

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) andmore » 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.« less

Graphite intercalation compound with iodine as the major intercalate

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh; Kucera, Donald

1994-01-01

Halogenated graphite CBr(x)I(y) (I less than y/x less than 10) was made by exposing graphite materials to either pure Br2 or an I2/Br2/HBr mixture to initiate the reaction, and then to iodine vapor containing a small amount of Br2/HBr/IBr to complete the intercalation reaction. Wetting of the graphite materials by the I2/Br2/HBr mixture is needed to start the reaction, and a small amount of Br2/HBr/IBr is needed to complete the charge transfer between iodine and carbon. The interplanar spacings for the graphite materials need to be in the 3.35 to 3.41 A range. The X-ray diffraction data obtained from the halogenated HOPG indicate that the distance between the two carbon layers containing intercalate is 7.25 A. Electrical resistivity of the fiber product is from 3 to 6.5 times the pristine value, The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine-to-bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 percent to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to structural damage during subsequent fluorination to fabricate graphite fluoride fibers.

Processing of next generation weather radar-multisensor precipitation estimates and quantitative precipitation forecast data for the DuPage County streamflow simulation system

USGS Publications Warehouse

Bera, Maitreyee; Ortel, Terry W.

2018-01-12

The U.S. Geological Survey, in cooperation with DuPage County Stormwater Management Department, is testing a near real-time streamflow simulation system that assists in the management and operation of reservoirs and other flood-control structures in the Salt Creek and West Branch DuPage River drainage basins in DuPage County, Illinois. As part of this effort, the U.S. Geological Survey maintains a database of hourly meteorological and hydrologic data for use in this near real-time streamflow simulation system. Among these data are next generation weather radar-multisensor precipitation estimates and quantitative precipitation forecast data, which are retrieved from the North Central River Forecasting Center of the National Weather Service. The DuPage County streamflow simulation system uses these quantitative precipitation forecast data to create streamflow predictions for the two simulated drainage basins. This report discusses in detail how these data are processed for inclusion in the Watershed Data Management files used in the streamflow simulation system for the Salt Creek and West Branch DuPage River drainage basins.

KlenTaq polymerase replicates unnatural base pairs by inducing a Watson-Crick geometry.

PubMed

Betz, Karin; Malyshev, Denis A; Lavergne, Thomas; Welte, Wolfram; Diederichs, Kay; Dwyer, Tammy J; Ordoukhanian, Phillip; Romesberg, Floyd E; Marx, Andreas

2012-07-01

Many candidate unnatural DNA base pairs have been developed, but some of the best-replicated pairs adopt intercalated structures in free DNA that are difficult to reconcile with known mechanisms of polymerase recognition. Here we present crystal structures of KlenTaq DNA polymerase at different stages of replication for one such pair, dNaM-d5SICS, and show that efficient replication results from the polymerase itself, inducing the required natural-like structure.

Polysulfide intercalated layered double hydroxides for metal capture applications

DOEpatents

Kanatzidis, Mercouri G.; Ma, Shulan

2017-04-04

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

On lunisolar calendars and intercalation schemes in Southeast Asia

NASA Astrophysics Data System (ADS)

Gislén, Lars

2018-04-01

This is a survey of different calendar intercalation schemes, mainly in Southeast Asia. The Thai and Burmese Calendars, superficially very similar, are shown to have quite different and interesting intercalation schemes. We also investigate similarities between the original Burmese Calendar and the Romakasiddhânta from India.

Observation of self-regulating response in Li xM yMn 2-yO 4 (M=Mn, Ni): A study using density functional theory

NASA Astrophysics Data System (ADS)

Ragavendran, K.; Sherwood, Daniel; Emmanuel, Bosco

2009-02-01

Density functional theory is used to understand the response of the transition metal-oxygen octahedra in Li xMn 2O 4 and Li xNi 0.5Mn 1.5O 4 to lithium intercalation and de-intercalation. Electronic structure computations on these compounds for x=0, 0.5 and 1 indicate that the 3d DOS of Mn is almost unaffected to variations in x. On the other hand, the oxygen 2p-DOS and to a lesser extent Ni 3d DOS are found to be sensitive to perturbation. The observations are explained on the grounds of self-regulating response, characteristic of systems having localized d states that communicate with a covalent manifold.

Montmorillonite-Alginate Composites as a Drug delivery System: Intercalation and In vitro Release of Diclofenac sodium

PubMed Central

Kevadiya, B. D.; Patel, H. A.; Joshi, G. V.; Abdi, S. H. R.; Bajaj, H. C.

2010-01-01

Diclofenac sodium and alginate was intercalated into montmorillonite to form uniform sized beads by gelation method. The structure and surface morphology of the synthesized composite beads were characterized by powdered X-ray diffraction, Fourier transform infrared spectroscopy, thermo gravimetric analysis and scanning electron microscopy. Diclofenac release kinetics of the composite in simulated intestinal fluid medium (pH 7.4) and effect of montmorillonite content on the in vitro release of diclofenac from diclofenac-montmorillonite-alginate composites bead was investigated by UV/Vis spectrophotometer. Diclofenac encapsulation efficiency in the montmorillonite-alginate composites bead increases with an increase in the montmorillonite content. The control release of diclofenac from diclofenac-montmorillonite-alginate composites beads was observed to be better as compared to diclofenac-alginate beads. PMID:21969745

Synthesis and characterization of lithium intercalation electrodes based on iron oxide thin films

NASA Astrophysics Data System (ADS)

Sarradin, J.; Guessous, A.; Ribes, M.

Sputter-deposited iron oxide thin films are investigated as a possible negative electrode for rocking-chair microbatteries. Experimental conditions related to the manufacturing of amorphous thin films suitable to a large number of available intercalation sites are described. Structural and physical properties of the thin layer films are presented. The conductivities of the amorphous thin films were found to be very high compared with those of the respective crystalline forms. Regarding the electrochemical behaviour, Fe 2O 3-based thin films electrodes are able to store and reversibly exchange lithium ions. At a C/2 charge/discharge rate with 100% depth-of-discharge (DOD), the specific capacity of these amorphous thin film electrodes remains almost constant and close to 330 Ah/kg after more than 120 charge/discharge cycles.

A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry.

PubMed

Lu, Ke; Hu, Ziyu; Ma, Jizhen; Ma, Houyi; Dai, Liming; Zhang, Jintao

2017-09-13

Graphitic carbons have been used as conductive supports for developing rechargeable batteries. However, the classic ion intercalation in graphitic carbon has yet to be coupled with extrinsic redox reactions to develop rechargeable batteries. Herein, we demonstrate the preparation of a free-standing, flexible nitrogen and phosphorus co-doped hierarchically porous graphitic carbon for iodine loading by pyrolysis of polyaniline coated cellulose wiper. We find that heteroatoms could provide additional defect sites for encapsulating iodine while the porous carbon skeleton facilitates redox reactions of iodine and ion intercalation. The combination of ion intercalation with redox reactions of iodine allows for developing rechargeable iodine-carbon batteries free from the unsafe lithium/sodium metals, and hence eliminates the long-standing safety issue. The unique architecture of the hierarchically porous graphitic carbon with heteroatom doping not only provides suitable spaces for both iodine encapsulation and cation intercalation but also generates efficient electronic and ionic transport pathways, thus leading to enhanced performance.Carbon-based electrodes able to intercalate Li + and Na + ions have been exploited for high performing energy storage devices. Here, the authors combine the ion intercalation properties of porous graphitic carbons with the redox chemistry of iodine to produce iodine-carbon batteries with high reversible capacities.

Resistivity of Carbon-Carbon Composites Halved

NASA Technical Reports Server (NTRS)

Gaier, James R.

2004-01-01

Carbon-carbon composites have become the material of choice for applications requiring strength and stiffness at very high temperatures (above 2000 C). These composites comprise carbon or graphite fibers embedded in a carbonized or graphitized matrix. In some applications, such as shielding sensitive electronics in very high temperature environments, the performance of these materials would be improved by lowering their electrical resistivity. One method to lower the resistivity of the composites is to lower the resistivity of the graphite fibers, and a proven method to accomplish that is intercalation. Intercalation is the insertion of guest atoms or molecules into a host lattice. In this study the host fibers were highly graphitic pitch-based graphite fibers, or vapor-grown carbon fibers (VGCF), and the intercalate was bromine. Intercalation compounds of graphite are generally thought of as being only metastable, but it has been shown that the residual bromine graphite fiber intercalation compound is remarkably stable, resisting decomposition even at temperatures at least as high as 1000 C. The focus of this work was to fabricate composite preforms, determine whether the fibers they were made from were still intercalated with bromine after processing, and determine the effect on composite resistivity. It was not expected that the resistivity would be lowered as dramatically as with graphite polymer composites because the matrix itself would be much more conductive, but it was hoped that the gains would be substantial enough to warrant its use in high-performance applications. In a collaborative effort supporting a Space Act Agreement between the NASA Glenn Research Center and Applied Sciences, Inc. (Cedarville, OH), laminar preforms were fabricated with pristine and bromine-intercalated pitch-based fibers (P100 and P100-Br) and VGCF (Pyro I and Pyro I-Br). The green preforms were carbonized at 1000 C and then heat treated to 3000 C. To determine whether the fibers in the samples were still intercalated after composite fabrication, they were subjected to X-ray diffraction. The composites containing intercalated graphite fibers showed much higher background scatter than that of pristine fibers, indicating the presence of bromine in the samples. More importantly, faint features indicative of intercalation were visible in the diffraction pattern, showing that the fibers were still intercalated.

Structure and Properties of Intercalated Graphite Fiber-Polymer Composites.

DTIC Science & Technology

1983-07-07

resistivities of all com- nal graphite. Experimental evidence (1,2) in- plexes were determined both before and after dicated that the electrophilic N02...others show promise as fluorinating agents in chemical synthesisI21. At this point, however, so little is Known of processing parameters and long-term

Morphology and Structure of Amino-fatty Acid Intercalated Montmorillonite

NASA Astrophysics Data System (ADS)

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 amino fatty acid, but decreased with increasing surfactant loading. This suggested that the amino fatty acid may be tethered to the clay structure via ionic interaction and/or ion-dipole attraction. Significant changes in the clay morphology, particle size and surface charge were observed after organo-modification. Scanning electron microscopy (SEM) revealed that the organo-clays have a disordered and flaky morphology, while the unmodified MMT appeared to be dispersed spherical grains. The effective (Z) diameter of Na+-MMT was found to be ~520 nm, but increased up to ~937 nm upon intercalation of 12-ALA. The zeta potential (ξ) of the clay materials, on the other hand, ranged from -33 mV for undmodified MMT to -16 mv (200CEC-AMMT clay). The possible occupational hazards of working with nanoclays should also be explored. Presently, the MTT-dye reduction assay was performed to determine cell viability of mouse monocyte-macrophages (J774A.1) after direct exposure to the clays. The cytotoxicity of the clays exhibited a chemistry and dose dependent response, with unmodified Na+-MMT as the most cytotoxic while the organo-clays exhibited low toxicity. These results demonstrated the successful intercalation of the surfactant for the production of organophilic clay materials for a wide range of applications.

Mechanisms and chemistry of dye adsorption on manganese oxides-modified diatomite.

PubMed

Al-Ghouti, Mohammad A; Al-Degs, Yehya S; Khraisheh, Majeda A M; Ahmad, Mohammad N; Allen, Stephen J

2009-08-01

The investigations into structural changes which occur during adsorbent modification and the adsorption mechanisms are essential for an effective design of adsorption systems. Manganese oxides were impregnated onto diatomite to form the type known as delta-birnessite. Initial investigations established the effectiveness of manganese oxides-modified diatomite (MOMD) to remove basic and reactive dyes from aqueous solution. The adsorption capacity of MOMD for methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was 320, 419, and 204mg/g, respectively. Various analytical techniques were used to characterise the structure and the mechanisms of the dye adsorption process onto MOMD such as Fourier transform infrared (FTIR), X-ray diffraction (XRD) and atomic absorption spectrometry (A.A.). A small shift to higher values of the d-spacing of dye/MOMD was observed indicating that a small amount of the dye molecules were intercalated in the MOMD structure and other molecules were adsorbed on the external surface of MOMD. Two mechanisms of dye adsorption onto MOMD were proposed; intercalation of the dye in the octahedral layers and adsorption of the dye on the MOMD external surface. Moreover, the results demonstrated that the MOMD structure was changed upon insertion of MB and RY with an obvious decrease in the intensity of the second main peak of the MOMD X-ray pattern.

Two-dimensional inorganic-organic perovskite hexagonal nanosheets: growth and mechanism

NASA Astrophysics Data System (ADS)

Shakya, Suman; Prakash, G. Vijaya

2015-03-01

In this era of novel technological materials, inorganic-organic (IO) materials has emerged as new class of materials for their application in photonic materials, miniaturized sensors, optoelectronic devices, non-linear optical apparatus by exploiting the properties of both constituents in a single entity. Here we present the formation and growth mechanism of two dimensional Inorganic-organic (IO) perovskite structures from anisotropically grown PbO hexagonal nanosheets, in three steps: Fabrication of hexagonal PbO nanosheets by the versatile bottom-up electrochemical deposition technique, iodinization of PbO into PbI2, followed by conversion of PbI2 into IO hybrid by the intercalation of organic moiety. A systematic and detailed structural study reveals that PbO nanosheet formation is more likely to result from an oriented attachment mechanism, in which the sheets formed by the reduction in surface area that happens during aggregation of small nanoparticle that each has a net dipole moment, which tends to form a self-assembled structure. Intercalation of organic moiety into the PbI2 layers yielded a selfassembled quantum-wells system of one of the IO hybrid, i.e. (C6H9C2H4NH3)2PbI4 (CHPI), sustaining the hexagonal shape.

TRPV2 is critical for the maintenance of cardiac structure and function in mice

PubMed Central

Katanosaka, Yuki; Iwasaki, Keiichiro; Ujihara, Yoshihiro; Takatsu, Satomi; Nishitsuji, Koki; Kanagawa, Motoi; Sudo, Atsushi; Toda, Tatsushi; Katanosaka, Kimiaki; Mohri, Satoshi; Naruse, Keiji

2014-01-01

The heart has a dynamic compensatory mechanism for haemodynamic stress. However, the molecular details of how mechanical forces are transduced in the heart are unclear. Here we show that the transient receptor potential, vanilloid family type 2 (TRPV2) cation channel is critical for the maintenance of cardiac structure and function. Within 4 days of eliminating TRPV2 from hearts of the adult mice, cardiac function declines severely, with disorganization of the intercalated discs that support mechanical coupling with neighbouring myocytes and myocardial conduction defects. After 9 days, cell shortening and Ca2+ handling by single myocytes are impaired in TRPV2-deficient hearts. TRPV2-deficient neonatal cardiomyocytes form no intercalated discs and show no extracellular Ca2+-dependent intracellular Ca2+ increase and insulin-like growth factor (IGF-1) secretion in response to stretch stimulation. We further demonstrate that IGF-1 receptor/PI3K/Akt pathway signalling is significantly downregulated in TRPV2-deficient hearts, and that IGF-1 administration partially prevents chamber dilation and impairment in cardiac pump function in these hearts. Our results improve our understanding of the molecular processes underlying the maintenance of cardiac structure and function. PMID:24874017

TRPV2 is critical for the maintenance of cardiac structure and function in mice.

PubMed

Katanosaka, Yuki; Iwasaki, Keiichiro; Ujihara, Yoshihiro; Takatsu, Satomi; Nishitsuji, Koki; Kanagawa, Motoi; Sudo, Atsushi; Toda, Tatsushi; Katanosaka, Kimiaki; Mohri, Satoshi; Naruse, Keiji

2014-05-29

The heart has a dynamic compensatory mechanism for haemodynamic stress. However, the molecular details of how mechanical forces are transduced in the heart are unclear. Here we show that the transient receptor potential, vanilloid family type 2 (TRPV2) cation channel is critical for the maintenance of cardiac structure and function. Within 4 days of eliminating TRPV2 from hearts of the adult mice, cardiac function declines severely, with disorganization of the intercalated discs that support mechanical coupling with neighbouring myocytes and myocardial conduction defects. After 9 days, cell shortening and Ca(2+) handling by single myocytes are impaired in TRPV2-deficient hearts. TRPV2-deficient neonatal cardiomyocytes form no intercalated discs and show no extracellular Ca(2+)-dependent intracellular Ca(2+) increase and insulin-like growth factor (IGF-1) secretion in response to stretch stimulation. We further demonstrate that IGF-1 receptor/PI3K/Akt pathway signalling is significantly downregulated in TRPV2-deficient hearts, and that IGF-1 administration partially prevents chamber dilation and impairment in cardiac pump function in these hearts. Our results improve our understanding of the molecular processes underlying the maintenance of cardiac structure and function.

Can Online Learning Communities Achieve the Goals of Traditional Professional Learning Communities? What the Literature Says. REL 2013-003

ERIC Educational Resources Information Center

Blitz, Cynthia L.

2013-01-01

For more than a decade practitioners have promoted professional learning communities (PLCs) as an effective structure for providing teachers with professional development (Chappuis, Chappuis, & Stiggins, 2009; DuFour, Eaker, & DuFour, 2005). These collaborative networks are believed to be effective because they expose teachers to new ideas…

Segmentation of the Striatum Using Data Fusion

DTIC Science & Technology

2001-10-25

palsy. Ann Neurol 1999; 45:1 65-74. [3] Barra V. in Fusion d’images 3D du cerveau : études de modèles et applications. Ph.D. Thesis, Université...in Segmentation des structure internes du cerveau . Ph. D. Thesis, Ecole Nationale Supérieure des Télécommunications, Paris (France), 1998. [15

Interlamellar adsorption of carbon dioxide by smectites

USGS Publications Warehouse

Fripiat, J.J.; Cruz, M.I.; Bohor, B.F.; Thomas, J.

1974-01-01

The adsorption of CO2 at low temperature (∼ −70°C) on thin films of homoionic smectites was studied by X-ray diffraction and by i.r. absorption. An increase in the d001 spacings of these clay films upon adsorption of CO2 was observed. In addition, a dichroic effect was readily discernible by comparing the i.r. spectra at two different orientations of the smectite films; i.e. with the film normal and tilted 35° with respect to the i.r. beam. The CO2 stretching vibration at 2350 cm−1 was used for the i.r. study. These observations conclusively show that CO2 intercalates the smectite structure rather than being adsorbed only in pores between clay tactoids—the limiting process proposed by other investigators.Adsorption isotherm data from earlier surface area studies are re-examined here through application of the Dubinin equation. Again, intercalation is demonstrated by convergence of the plotted experimental data for smectites containing large monovalent interlayer cations toward a pore volume that is near the calculated theoretical value for a monolayer of intercalated CO2.Scanning electron photomicrographs of Li- and Cs- smectites provide additional evidence that aggregation differences are not responsible for the large observed difference in BET surface areas obtained for these smectites with CO2 as the adsorbate. At low magnification, visual differences in macro-aggregates are apparent, but at high magnification no significant differences are observed in the micro-structure of individual aggregates where the major amount of gas adsorption really occurs.

A micrographic and gravimetric study of intercalation and deintercalation of graphite fibers

NASA Technical Reports Server (NTRS)

Hung, C. C.

1985-01-01

Intercalation and deintercalation of Union Carbide P-100 graphite fibers with liquid and vaporous bromine was studied gravimetrically and microscopically. The mass of the bromine intercalated fibers was found to be 17 to 20 percent greater than their pristine counterpart. This variation decreased to 17 to 18 percent after heating in air for 3 days at 200 C and to 14.5 to 18 percent after 6 days of 260 C heating. The fiber length did not change throughout the experiment. The fiber diameter increased during intercalation and decreased slightly upon deintercalation but was not affected by heating to 260 C for 3 days in air. Comparing the mass and volume data to those with highly oriented pyrolitic graphite or natural single crystal graphite suggested the possibility that the intercalated P-100 fibers could be mostly stage 4.

Synthesis of (Hexaconazole-Zinc/Aluminum-Layered Double Hydroxide Nanocomposite) Fungicide Nanodelivery System for Controlling Ganoderma Disease in Oil Palm.

PubMed

Mustafa, Isshadiba F; Hussein, Mohd Zobir; Saifullah, Bullo; Idris, Abu Seman; Hilmi, Nur Hailini Z; Fakurazi, Sharida

2018-01-31

A fungicide, hexaconazole was successfully intercalated into the intergalleries of zinc/aluminum-layered double hydroxide (ZALDH) using the ion-exchange method. Due to the intercalation of hexaconazole, the basal spacing of the ZALDH was increased from 8.7 Å in ZALDH to 29.4 Å in hexaconazole-intercalated ZALDH (HZALDH). The intercalation of hexaconazole into the interlayer of the nanocomposite was confirmed using the Fourier-transform infrared (FTIR) study. This supramolecular chemistry intercalation process enhanced the thermal stability of the hexaconazole moiety. The fungicide loading was estimated to be 51.8%. The nanodelivery system also shows better inhibition toward the Ganoderma boninense growth than the counterpart, free hexaconazole. The results from this work have a great potential to be further explored for combating basal stem rot (BSR) disease in oil palm plantation.

Intercalating dyes for enhanced contrast in second-harmonic generation imaging of protein crystals

PubMed Central

Newman, Justin A.; Scarborough, Nicole M.; Pogranichniy, Nicholas R.; Shrestha, Rashmi K.; Closser, Richard G.; Das, Chittaranjan; Simpson, Garth J.

2015-01-01

The second-harmonic generation (SHG) activity of protein crystals was found to be enhanced by up to ∼1000-fold by the intercalation of SHG phores within the crystal lattice. Unlike the intercalation of fluorophores, the SHG phores produced no significant background SHG from solvated dye or from dye intercalated into amorphous aggregates. The polarization-dependent SHG is consistent with the chromophores adopting the symmetry of the crystal lattice. In addition, the degree of enhancement for different symmetries of dyes is consistent with theoretical predictions based on the molecular nonlinear optical response. Kinetics studies indicate that intercalation arises over a timeframe of several minutes in lysozyme, with detectable enhancements within seconds. These results provide a potential means to increase the overall diversity of protein crystals and crystal sizes amenable to characterization by SHG microscopy. PMID:26143918

The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs)

NASA Astrophysics Data System (ADS)

Hogan, Greg Anthony

The process of molecular transport and intercalation has been widely studied for many years, resulting in the discovery of molecular frameworks that are capable of hosting guest molecules or ions. Layered and porous metal-organic frameworks (MOFs) have been found to have applications in the field of catalysis, storage, separations, and ion-exchange. More recently, molecular components with peripheral hydrogen-bonding moieties have been used to affect the synthesis of hydrogen-bonded metal-organic frameworks (HMOFs) as an alternative to MOFs, which are interconnected via coordinate-covalent bonds. While MOFs are perhaps stronger materials, HMOFs have the advantage of being easily modifiable and more flexible. Because HMOFs have not been extensively studied for their ability to host molecules, and because their ability to withstand guest loss and guest exchange is essentially unknown, here we report the synthesis and molecular transport properties of both close-packed and porous HMOFs. Layered materials can mimic the behavior of naturally occurring clays, where guest molecules are absorbed and the layer will expand to accommodate the entering guest molecule. We have created a clay mimic composed of a metal pyridine-dicarboxylates and ammonium counterions (a layered HMOF), which is suitable for studying the ability of such materials to absorb guest molecules. We can control the distance of the interlayer region, as well as the chemical nature (hydrophobic or hydrophilic) by varying the organic amine. The metal complex contains axial water ligands that are replaceable, and such ligand exchange has precedence in coordination polymer (MOF) systems, and has been termed "coordinative intercalation". Using the synthesized layered material we examined the process of intercalation, having chosen a variety of guest molecules ranging from alkyl to aryl molecules, each of which have substituents varying in size, shape and electronics. The first set of guest molecules are non-coordinating and are theoretically capable of entering the layer and anchoring freely through the use of non-covalent interactions. The second set of guest molecules contain a pyridine moiety that can exchange with the coordinated water ligand through coordinative-intercalation. The products have been characterized by TGA, DSC, UV-Vis, and powder XRD. Further work was dedicated to examining porous materials, which were created using organic diamines, rather than simple primary amines, as starting materials. The resulting diammonium cations act as pillars, forming open channels. The predefined channel dimensions allow the insertion of specific sized guest molecules. The walls of the channel are close-packed, so that in theory guest molecules can travel in one direction through the solid. Using the synthesized pillared structure we investigated guest inclusion and selectivity through the process of co-crystallization. The stability of the pillared structure in the absence of guests is also reported, as well as the potential for the empty pillared structure to withstand guest re-insertion and removal.

IR study of dickite-formamide intercalate, Al 2Si 2O 5(OH) 4-H 2NCOH

NASA Astrophysics Data System (ADS)

Zamama, M.; Knidiri, Mohamed

2000-05-01

Direct intercalation of formamide (FAM) in dickite occurs spontaneously when samples are treated by ultrason. The X-ray diffraction patterns show that this intercalation increases the d 001 spacing from 7.19 to 10.77 Å. It is concluded from infrared studies that hydrogen bonds are formed between CO groups of formamide and inner surface hydroxyls of dickite, indicated by the shift of the hydroxyl bands from 3708, 3654 cm -1 and 3622 for natural dickite to 3575, 3520, 3450 and 3612 cm -1 for FAM-intercalated dickite.

IR study of dickite-formamide intercalate, Al2Si2O5(OH)4-H2NCOH.

PubMed

Zamama, M; Knidiri, M

2000-05-01

Direct intercalation of formamide (FAM) in dickite occurs spontaneously when samples are treated by ultrason. The X-ray diffraction patterns show that this intercalation increases the d001 spacing from 7.19 to 10.77 A. It is concluded from infrared studies that hydrogen bonds are formed between C=O groups of formamide and inner surface hydroxyls of dickite, indicated by the shift of the hydroxyl bands from 3708, 3654 cm(-1) and 3622 for natural dickite to 3575, 3520, 3450 and 3612 cm(-1) for FAM-intercalated dickite.

Thin-walled nanoscrolls by multi-step intercalation from tubular halloysite-10 Å and its rearrangement upon peroxide treatment

NASA Astrophysics Data System (ADS)

Zsirka, Balázs; Horváth, Erzsébet; Szabó, Péter; Juzsakova, Tatjána; Szilágyi, Róbert K.; Fertig, Dávid; Makó, Éva; Varga, Tamás; Kónya, Zoltán; Kukovecz, Ákos; Kristóf, János

2017-03-01

Surface modification of the halloysite-10 Å mineral with tubular morphology can be achieved by slightly modified procedures developed for the delamination of kaolinite minerals. The resulting delaminated halloysite nanoparticles have unexpected surface/morphological properties that display, new potentials in catalyst development. In this work, a four-step intercalation/delamination procedure is described for the preparation of thin-walled nanoscrolls from the multi-layered hydrated halloysite mineral that consists of (1) intercalation of halloysite with potassium acetate, (2) replacement intercalation with ethylene glycol, (3) replacement intercalation with hexylamine, and (4) delamination with toluene. The intercalation steps were followed by X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption, thermogravimetry, and infrared spectroscopy. Delamination eliminated the crystalline order and the crystallite size along the 'c'-axis, increased the specific surface area, greatly decreased the thickness of the mineral tubes to a monolayer, and shifted the pore diameter toward the micropore region. Unexpectedly, the removal of residual organics from intercalation steps adsorbed at the nanoscroll surface with a peroxide treatment resulted in partial recovery of crystallinity and increase of crystallite size along the 'c'-crystal direction. The d(001) value showed a diffuse pattern at 7.4-7.7 Å due to the rearrangement of the thin-walled nanoscrolls toward the initial tubular morphology of the dehydrated halloysite-7 Å mineral.

CDC-42 Orients Cell Migration during Epithelial Intercalation in the Caenorhabditis elegans Epidermis.

PubMed

Walck-Shannon, Elise; Lucas, Bethany; Chin-Sang, Ian; Reiner, David; Kumfer, Kraig; Cochran, Hunter; Bothfeld, William; Hardin, Jeff

2016-11-01

Cell intercalation is a highly directed cell rearrangement that is essential for animal morphogenesis. As such, intercalation requires orchestration of cell polarity across the plane of the tissue. CDC-42 is a Rho family GTPase with key functions in cell polarity, yet its role during epithelial intercalation has not been established because its roles early in embryogenesis have historically made it difficult to study. To circumvent these early requirements, in this paper we use tissue-specific and conditional loss-of-function approaches to identify a role for CDC-42 during intercalation of the Caenorhabditis elegans dorsal embryonic epidermis. CDC-42 activity is enriched in the medial tips of intercalating cells, which extend as cells migrate past one another. Moreover, CDC-42 is involved in both the efficient formation and orientation of cell tips during cell rearrangement. Using conditional loss-of-function we also show that the PAR complex functions in tip formation and orientation. Additionally, we find that the sole C. elegans Eph receptor, VAB-1, functions during this process in an Ephrin-independent manner. Using epistasis analysis, we find that vab-1 lies in the same genetic pathway as cdc-42 and is responsible for polarizing CDC-42 activity to the medial tip. Together, these data establish a previously uncharacterized role for polarized CDC-42, in conjunction with PAR-6, PAR-3 and an Eph receptor, during epithelial intercalation.

CDC-42 Orients Cell Migration during Epithelial Intercalation in the Caenorhabditis elegans Epidermis

PubMed Central

Lucas, Bethany; Chin-Sang, Ian; Reiner, David; Kumfer, Kraig

2016-01-01

Cell intercalation is a highly directed cell rearrangement that is essential for animal morphogenesis. As such, intercalation requires orchestration of cell polarity across the plane of the tissue. CDC-42 is a Rho family GTPase with key functions in cell polarity, yet its role during epithelial intercalation has not been established because its roles early in embryogenesis have historically made it difficult to study. To circumvent these early requirements, in this paper we use tissue-specific and conditional loss-of-function approaches to identify a role for CDC-42 during intercalation of the Caenorhabditis elegans dorsal embryonic epidermis. CDC-42 activity is enriched in the medial tips of intercalating cells, which extend as cells migrate past one another. Moreover, CDC-42 is involved in both the efficient formation and orientation of cell tips during cell rearrangement. Using conditional loss-of-function we also show that the PAR complex functions in tip formation and orientation. Additionally, we find that the sole C. elegans Eph receptor, VAB-1, functions during this process in an Ephrin-independent manner. Using epistasis analysis, we find that vab-1 lies in the same genetic pathway as cdc-42 and is responsible for polarizing CDC-42 activity to the medial tip. Together, these data establish a previously uncharacterized role for polarized CDC-42, in conjunction with PAR-6, PAR-3 and an Eph receptor, during epithelial intercalation. PMID:27861585

An intercalated BSc degree is associated with higher marks in subsequent medical school examinations.

PubMed

Cleland, Jennifer A; Milne, Andrew; Sinclair, Hazel; Lee, Amanda J

2009-05-19

To compare medical students on a modern MBChB programme who did an optional intercalated degree with their peers who did not intercalate; in particular, to monitor performance in subsequent undergraduate degree exams. This was a retrospective, observational study of anonymised databases of medical student assessment outcomes. Data were accessed for graduates, University of Aberdeen Medical School, Scotland, UK, from the years 2003 to 2007 (n = 861). The main outcome measure was marks for summative degree assessments taken after intercalating. Of 861 medical students, 154 (17.9%) students did an intercalated degree. After adjustment for cohort, maturity, gender and baseline (3rd year) performance in matching exam type, having done an IC degree was significantly associated with attaining high (18-20) common assessment scale (CAS) marks in three of the six degree assessments occurring after the IC students rejoined the course: the 4th year written exam (p < 0.001), 4th year OSCE (p = 0.001) and the 5th year Elective project (p = 0.010). Intercalating was associated with improved performance in Years 4 and 5 of the MBChB. This improved performance will further contribute to higher academic ranking for Foundation Year posts. Long-term follow-up is required to identify if doing an optional intercalated degree as part of a modern medical degree is associated with following a career in academic medicine.

An intercalated BSc degree is associated with higher marks in subsequent medical school examinations

PubMed Central

Cleland, Jennifer A; Milne, Andrew; Sinclair, Hazel; Lee, Amanda J

2009-01-01

Background To compare medical students on a modern MBChB programme who did an optional intercalated degree with their peers who did not intercalate; in particular, to monitor performance in subsequent undergraduate degree exams. Methods This was a retrospective, observational study of anonymised databases of medical student assessment outcomes. Data were accessed for graduates, University of Aberdeen Medical School, Scotland, UK, from the years 2003 to 2007 (n = 861). The main outcome measure was marks for summative degree assessments taken after intercalating. Results Of 861 medical students, 154 (17.9%) students did an intercalated degree. After adjustment for cohort, maturity, gender and baseline (3rd year) performance in matching exam type, having done an IC degree was significantly associated with attaining high (18–20) common assessment scale (CAS) marks in three of the six degree assessments occurring after the IC students rejoined the course: the 4th year written exam (p < 0.001), 4th year OSCE (p = 0.001) and the 5th year Elective project (p = 0.010). Conclusion Intercalating was associated with improved performance in Years 4 and 5 of the MBChB. This improved performance will further contribute to higher academic ranking for Foundation Year posts. Long-term follow-up is required to identify if doing an optional intercalated degree as part of a modern medical degree is associated with following a career in academic medicine. PMID:19454007

Acceptor-type hydroxide graphite intercalation compounds electrochemically formed in high ionic strength solutions.

PubMed

Miyazaki, Kohei; Iizuka, Asuka; Mikata, Koji; Fukutsuka, Tomokazu; Abe, Takeshi

2017-09-05

The intercalation of hydroxide ions (OH - ) into graphite formed graphite intercalation compounds (GICs) in high ionic strength solutions. GICs of solvated OH - anions with two water molecules (OH - ·2H 2 O) in alkaline aqueous solutions and GICs of only OH - anions in a molten NaOH-KOH salt solution were electrochemically synthesized.

Bonding between graphene and MoS 2 monolayers without and with Li intercalation

DOE PAGES

Ahmed, Towfiq; Modine, N. A.; Zhu, Jian-Xin

2015-07-27

We performed density functional theory (DFT) calculations for a bi-layered heterostructure combining a graphene layer with a MoS 2 layer with and without intercalated Li atoms. Our calculations demonstrate the importance of the van der Waals (vdW) interaction, which is crucial for forming stable bonding between the layers. Our DFT calculation correctly reproduces the linear dispersion, or Dirac cone, feature at the Fermi energy for the isolated graphene monolayer and the band gap for the MoS 2 monolayer. For the combined graphene/MoS 2 bi-layer, we observe interesting electronic structure and density of states (DOS) characteristics near the Fermi energy, showingmore » both the gap like features of the MoS 2 layer and in-gap states with linear dispersion contributed mostly by the graphene layer. Our calculated total DOS in this vdW heterostructure reveals that the graphene layer significantly contributes to pinning the Fermi energy at the center of the band gap of MoS 2. We also find that intercalating Li ions in between the layers of the graphene/MoS2 heterostructure enhances the binding energy through orbital hybridizations between cations (Li adatoms) and anions (graphene and MoS 2 monolayers). Moreover, we calculate the dielectric function of the Li intercalated graphene/MoS 2 heterostructure, the imaginary component of which can be directly compared with experimental measurements of optical conductivity in order to validate our theoretical prediction. We observe sharp features in the imaginary component of the dielectric function, which shows the presence of a Drude peak in the optical conductivity, and therefore metallicity in the lithiated graphene/MoS 2 heterostructure.« less

Intercalation of aflatoxin B sub 1 in two oligodeoxynucleotide adducts: Comparative sup 1 H NMR analysis of d(ATC sup AFB GAT)ter dot d(ATCGAT) and d(AT sup ATB GCAT) sub 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gopalakrishnan, S.; Harris, T.M.; Stone, M.P.

8,9-Dihydro-8-(N7-guanyl-(d(ATCGAT)))-9-hydroxyaflatoxin B{sub 1}{center dot}d(ATCGAT) and 8,9-dihydro-8-(N7-guanyl-(d(ATGCAT)))-9-hydroxyafltoxin B{sub 1}{center dot}8,9-dihydro-8-(N7-guanyl-(d(ATGCAT)))-9-hydroxyaflatoxin B{sub 1} were prepared by direct addition of aflatoxin B{sub 1} 8,9-expoxide to d(ATCGAT){sub 2} and d(ATGCAT){sub 2}, respectively. {sup 1}H NOE experiments, nonselective {sup 1}H T{sub 1} relaxation measurements, and {sup 1}H chemical shift perturbations demonstrate that in both modified oligodeoxynucleotides the aflatoxin moiety is intercalated above the 5{prime}-face of the modified guanine. The oligodeoxynucleotides remain right-handed, and perturbation of the B-DNA structure is localized adjacent to the adducted guanine. Aflatoxin-oligodeoxynucleotide {sup 1}H NOEs are observed between aflatoxin and the 5{prime}-neighbor base pair and include both the major groove andmore » the minor groove. The protons at C8 and C9 of the aflatoxin terminal furan ring exhibit slower spin-lattice relaxation as compared to other oligodeoxynucleotide protons, which supports the conclusion that they face into the major groove. Increased shielding is observed for aflatoxin protons. The difference in reaction stoichiometry is consistent with an intercalated transition-state complex between aflatoxin B{sub 1} 8,9-epoxide and B-DNA. Intercalation provides excellent positioning for nucleophilic attack by guanine N7 on aflatoxin B{sub 1} 8,9-epoxide, which probably accounts for the observed efficiency of adduct formation despite the relatively low DNA binding affinity observed for aflatoxin B{sub 1}.« less

Hydrophobic Modification of Layered Clays and Compatibility for Epoxy Nanocomposites

PubMed Central

Lin, Jiang-Jen; Chan, Ying-Nan; Lan, Yi-Fen

2010-01-01

Recent studies on the intercalation and exfoliation of layered clays with polymeric intercalating agents involving poly(oxypropylene)-amines and the particular uses for epoxy nanocomposites are reviewed. For intercalation, counter-ionic exchange reactions of clays including cationic layered silicates and anionic Al-Mg layered double hydroxide (LDH) with polymeric organic ions afforded organoclays led to spatial interlayer expansion from 12 to 92 Å (X-ray diffraction) as well as hydrophobic property. The inorganic clays of layered structure could be modified by the poly(oxypropylene)amine-salts as the intercalating agents with molecular weights ranging from 230 to 5,000 g/mol. Furthermore, natural montmorillonite (MMT) clay could be exfoliated into thin layer silicate platelets (ca. 1 nm thickness) in one step by using polymeric types of exfoliating agents. Different lateral dimensions of MMT, synthetic fluorinated Mica and LDH clays had been cured into epoxy nanocomposites. The hydrophobic amine-salt modification resulting in high spacing of layered or exfoliation of individual clay platelets is the most important factor for gaining significant improvements of properties. In particular, these modified clays were reported to gain significant improvements such as reduced coefficient of thermal expansion (CTE), enhanced thermal stability, and hardness. The utilization of these layered clays for initiating the epoxy self-polymerization was also reported to have a unique compatibility between clay and organic resin matrix. However, the matrix domain lacks of covalently bonded crosslink and leads to the isolation of powder material. It is generally concluded that the hydrophobic expansion of the clay inter-gallery spacing is the crucial step for enhancing the compatibility and the ultimate preparation of the advanced epoxy materials.

Large-scale symmetry-adapted perturbation theory computations via density fitting and Laplace transformation techniques: investigating the fundamental forces of DNA-intercalator interactions.

PubMed

Hohenstein, Edward G; Parrish, Robert M; Sherrill, C David; Turney, Justin M; Schaefer, Henry F

2011-11-07

Symmetry-adapted perturbation theory (SAPT) provides a means of probing the fundamental nature of intermolecular interactions. Low-orders of SAPT (here, SAPT0) are especially attractive since they provide qualitative (sometimes quantitative) results while remaining tractable for large systems. The application of density fitting and Laplace transformation techniques to SAPT0 can significantly reduce the expense associated with these computations and make even larger systems accessible. We present new factorizations of the SAPT0 equations with density-fitted two-electron integrals and the first application of Laplace transformations of energy denominators to SAPT. The improved scalability of the DF-SAPT0 implementation allows it to be applied to systems with more than 200 atoms and 2800 basis functions. The Laplace-transformed energy denominators are compared to analogous partial Cholesky decompositions of the energy denominator tensor. Application of our new DF-SAPT0 program to the intercalation of DNA by proflavine has allowed us to determine the nature of the proflavine-DNA interaction. Overall, the proflavine-DNA interaction contains important contributions from both electrostatics and dispersion. The energetics of the intercalator interaction are are dominated by the stacking interactions (two-thirds of the total), but contain important contributions from the intercalator-backbone interactions. It is hypothesized that the geometry of the complex will be determined by the interactions of the intercalator with the backbone, because by shifting toward one side of the backbone, the intercalator can form two long hydrogen-bonding type interactions. The long-range interactions between the intercalator and the next-nearest base pairs appear to be negligible, justifying the use of truncated DNA models in computational studies of intercalation interaction energies.

Large-scale symmetry-adapted perturbation theory computations via density fitting and Laplace transformation techniques: Investigating the fundamental forces of DNA-intercalator interactions

NASA Astrophysics Data System (ADS)

Hohenstein, Edward G.; Parrish, Robert M.; Sherrill, C. David; Turney, Justin M.; Schaefer, Henry F.

2011-11-01

Symmetry-adapted perturbation theory (SAPT) provides a means of probing the fundamental nature of intermolecular interactions. Low-orders of SAPT (here, SAPT0) are especially attractive since they provide qualitative (sometimes quantitative) results while remaining tractable for large systems. The application of density fitting and Laplace transformation techniques to SAPT0 can significantly reduce the expense associated with these computations and make even larger systems accessible. We present new factorizations of the SAPT0 equations with density-fitted two-electron integrals and the first application of Laplace transformations of energy denominators to SAPT. The improved scalability of the DF-SAPT0 implementation allows it to be applied to systems with more than 200 atoms and 2800 basis functions. The Laplace-transformed energy denominators are compared to analogous partial Cholesky decompositions of the energy denominator tensor. Application of our new DF-SAPT0 program to the intercalation of DNA by proflavine has allowed us to determine the nature of the proflavine-DNA interaction. Overall, the proflavine-DNA interaction contains important contributions from both electrostatics and dispersion. The energetics of the intercalator interaction are are dominated by the stacking interactions (two-thirds of the total), but contain important contributions from the intercalator-backbone interactions. It is hypothesized that the geometry of the complex will be determined by the interactions of the intercalator with the backbone, because by shifting toward one side of the backbone, the intercalator can form two long hydrogen-bonding type interactions. The long-range interactions between the intercalator and the next-nearest base pairs appear to be negligible, justifying the use of truncated DNA models in computational studies of intercalation interaction energies.

Structure post-flambée pour la locomotion d'un microrobot intratubulaire: comparaison modèle-expérience de l'effort de serrage dans le tube

NASA Astrophysics Data System (ADS)

Libersa, C.; Arsicault, M.; Lallemand, J.-P.

2002-12-01

Ces travaux entrent dans le cadre des études nécessaires à la mise au point d'une structure déformable actionnée par fils en alliage à mémoire de forme. L'application visée est son utilisation comme module de locomotion d'un microrobot intratubulaire autonome de type “ lombric ”. Un module est constitué d'un cadre élastique carré forcé en post-flambement sur un squelette rigide, de manière à obtenir deux configurations symétriques d'équilibre stable correspondant au premier mode de flambage. Le passage d'un état d'équilibre à l'autre est obtenu par la contraction de fils AMF éduqués disposés sur le cadre post-flambé. Un assemblage par juxtaposition de cinq modules identiques compose le corps du microrobot. Suivant un cycle de locomotion adéquat, chacun de ces actionneurs “ tout ou rien ” permet la prise d'appui sur les parois du tube ou l'allongement local nécessaire à l'avance du microrobot. Nous présentons ici les résultats obtenus lors d'un chargement transversal d'un module, et en particulier les courbes reliant l'effort de réaction et le déplacement du point en contact avec le tube. L'influence du serrage subit par le module sur le maintien du microrobot dans un tube vertical est déterminée. Les résultats expérimentaux obtenus sont comparés avec les résultats numériques.

Effets non lineaires transversaux dans les guides d'ondes plans

NASA Astrophysics Data System (ADS)

Dumais, Patrick

Les effets non lineaires transversaux dus a l'effet Kerr optique non resonant sont etudies dans deux types de guides a geometrie plane. D'abord (au chapitre 2), l'emission de solitons spatiaux d'un guide de type canal est etudie historiquement, analytiquement et numeriquement dans le but d'en faire la conception et la fabrication, en AlGaAs, dans la region spectrale en deca de la moitie de la bande interdite de ce materiau, soit autour de 1,5 microns. Le composant, tel que concu, comporte une structure de multipuits quantiques. Le desordonnement local de cette structure permet une variation locale du coefficient Kerr dans le guide, ce qui mene a l'emission d'un soliton spatial au-dela d'une puissance optique de seuil. L'observation experimentale d'un changement en fonction de l'intensite du profil de champ a la sortie du guide realise est presentee. Deuxiemement (au chapitre 3) une technique de mesure du coefficient Kerr dans un guide plan est presentee. Cette technique consiste a mesurer le changement de transmission au travers d'un cache place a la sortie du guide en fonction de l'intensite crete a l'entree du guide plan. Une methode pour determiner les conditions optimales pour la sensibilite de la mesure est presentee, illustree de plusieurs exemples. Finalement, la realisation d'un oscillateur parametrique optique basee sur un cristal de niobate de lithium a domaines periodiquement inverses est presentee. La theorie des oscillateurs parametriques optiques est exposee avec une emphase sur la generation d'impulsions intenses a des longueurs d'onde autour de 1,5 microns a partir d'un laser Ti:saphir, dans le but d'obtenir une source pour faire les experiences sur l'emission solitonique.

Elaboration du Ge mesoporeux et etude de ses proprietes physico-chimiques en vue d'applications photovoltaiques

NASA Astrophysics Data System (ADS)

Tutashkonko, Sergii

Le sujet de cette these porte sur l'elaboration du nouveau nanomateriau par la gravure electrochimique bipolaire (BEE) --- le Ge mesoporeux et sur l'analyse de ses proprietes physico-chimiques en vue de son utilisation dans des applications photovoltaiques. La formation du Ge mesoporeux par gravure electrochimique a ete precedemment rapportee dans la litterature. Cependant, le verrou technologique important des procedes de fabrication existants consistait a obtenir des couches epaisses (superieure a 500 nm) du Ge mesoporeux a la morphologie parfaitement controlee. En effet, la caracterisation physico-chimique des couches minces est beaucoup plus compliquee et le nombre de leurs applications possibles est fortement limite. Nous avons developpe un modele electrochimique qui decrit les mecanismes principaux de formation des pores ce qui nous a permis de realiser des structures epaisses du Ge mesoporeux (jusqu'au 10 mum) ayant la porosite ajustable dans une large gamme de 15% a 60%. En plus, la formation des nanostructures poreuses aux morphologies variables et bien controlees est desormais devenue possible. Enfin, la maitrise de tous ces parametres a ouvert la voie extremement prometteuse vers la realisation des structures poreuses a multi-couches a base de Ge pour des nombreuses applications innovantes et multidisciplinaires grace a la flexibilite technologique actuelle atteinte. En particulier, dans le cadre de cette these, les couches du Ge mesoporeux ont ete optimisees dans le but de realiser le procede de transfert de couches minces d'une cellule solaire a triple jonctions via une couche sacrificielle en Ge poreux. Mots-cles : Germanium meso-poreux, Gravure electrochimique bipolaire, Electrochimie des semi-conducteurs, Report des couches minces, Cellule photovoltaique

XRD, SEM and infrared study into the intercalation of sodium hexadecyl sulfate (SHS) into hydrocalumite.

PubMed

Zhang, Ping; Wang, Tianqi; Zhang, Longlong; Wu, Daishe; Frost, Ray L

2015-12-05

Hydrocalumite (CaAl-LDH-Cl) interacted with a natural anionic surfactant, sodium hexadecyl sulfate (SHS), was performed using an intercalation method. To understand the intercalation behavior and characterize the resulting products, powder X-ray diffraction (XRD), scan electron microscopy (SEM) and mid-infrared (MIR) spectroscopy combined with near-infrared (NIR) spectroscopy technique were used. The XRD analysis indicated that SHS was intercalated into CaAl-LDH-Cl successfully, resulting in an expansion of the interlayer (from 0.78 nm to 2.74 nm). The bands of C-H stretching vibrations of SHS were observed in the near-infrared spectra, which indicated that the resulting products were indeed CaAl-LDH-SHS. In addition, the bands of water stretching vibrations and OH groups shifted to higher wavenumbers when SHS was intercalated into CaAl-LDH-Cl interlayer space. Copyright © 2015 Elsevier B.V. All rights reserved.

Calcium intercalation into layered fluorinated sodium iron phosphate

DOE PAGES

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei; ...

2017-10-09

Here, the energy density and cost of battery systems could be improved by moving to alternative battery chemistries such as Ca-ion. However, in order to switch chemistries many problems need to be solved including the identification of cathode materials with high energy density, and electrolytes that can plate and strip calcium metal. Herein, the feasibility and cycling performance of Ca 2+ intercalation into a desodiated layered Na 2FePO 4F host is described. This is the first demonstration of Ca 2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca 2+ intercalation. Althoughmore » substantial effort is still needed to identify a high energy density cathode material, this study and others demonstrate the feasibility of Ca 2+ intercalation into multiple materials making it more probable that such a cathode material can be found.« less

Calcium intercalation into layered fluorinated sodium iron phosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei

Here, the energy density and cost of battery systems could be improved by moving to alternative battery chemistries such as Ca-ion. However, in order to switch chemistries many problems need to be solved including the identification of cathode materials with high energy density, and electrolytes that can plate and strip calcium metal. Herein, the feasibility and cycling performance of Ca 2+ intercalation into a desodiated layered Na 2FePO 4F host is described. This is the first demonstration of Ca 2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca 2+ intercalation. Althoughmore » substantial effort is still needed to identify a high energy density cathode material, this study and others demonstrate the feasibility of Ca 2+ intercalation into multiple materials making it more probable that such a cathode material can be found.« less

Supramolecular polymer formation by cyclic dinucleotides and intercalators affects dinucleotide enzymatic processing

PubMed Central

Nakayama, Shizuka; Zhou, Jie; Zheng, Yue; Szmacinski, Henryk; Sintim, Herman O

2016-01-01

Background: Cyclic dinucleotides form supramolecular aggregates with intercalators, and this property could be utilized in nanotechnology and medicine. Methods & results: Atomic force microscopy and electrophoretic mobility shift assays were used to show that cyclic diguanylic acid (c-di-GMP) forms G-wires in the presence of intercalators. The average fluorescence lifetime of thiazole orange, when bound to c-di-GMP was greater than when bound to DNA G-quadruplexes or dsDNA. The stability of c-di-GMP supramolecular polymers is dependent on both the nature of the cation present and the intercalator. C-di-GMP or cyclic diadenylic acid/intercalator complexes are more resistant to cleavage by YybT, a phosphodiesterase, than the uncomplexed nucleotides. Conclusion: Cleavage of bacterial cyclic dinucleotides could be slowed down via complexation with small molecules and that this could be utilized for diverse applications in nanotechnology and medicine. PMID:28031943

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

PubMed

Marangoni, Rafael; Mikowski, Alexandre; Wypych, Fernando

2010-11-15

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

RLE (Research Laboratory of Electronics) Progress Report Number 129.

DTIC Science & Technology

1987-01-01

8217," ’,/’.’t MICROCOP ,"Y RESOLUTION TEST C-’HA"-/’%’.’."."% "-’- -" "."o -- - -" " OI FILE COPYAJ MASSACHUSETTS INSTITUTE OF EHOGYD The RESEARCH LABORATORY of...Intercalation Compound Structures and Transitions .................................. 59 10.0 Semiconductor Surface Studies...understanding of the HEMT, which is the basic block in building surface superlattices on III-V compound materials, our device structure has been simu

Étude par RMN à l'état solide de catalyseurs oxydes du type Mo-P-Al

NASA Astrophysics Data System (ADS)

Quartararo, J.; Rigole, M.; Guelton, M.; Amoureux, J. P.; Grimblot, J.

1999-10-01

Solid state 27Al NMR and especially 27Al MQMAS is used to characterize the oxide Mo-P-Al hydrotreating catalysts. This application shows that NMR is an efficient method to determine the local structure of the elements in the amorphous catalysts. So, this permits to conclude that the association of the Mo and the P leads to the formation of aluminium phosphates and that differences in the structure depend on the method of preparation. La RMN du solide et notamment la méthode “MQMAS" de 27Al est utilisée pour caractériser en détail les catalyseurs d'hydrotraitement du type Mo-P-Al sous forme oxyde. Cette application montre que la RMN est un outil efficace pour déterminer la structure locale des éléments introduits dans les catalyseurs de caractère amorphe. Ainsi, elle permet d'établir que le Mo associé au P induit la formation de phosphates d'aluminium. Des différences de structure en fonction de la méthode de préparation sont également observées.

Electrochemical lithium intercalation into Bi2Sr2CaCu2O8+δ

NASA Astrophysics Data System (ADS)

Shimono, Takahiro; Kobayashi, Wataru; Nitani, Hiroaki; Kumai, Reiji; Moritomo, Yutaka

2013-04-01

We have prepared Li-intercalated LixBi2Sr2CaCu2O8+δ (x =0-2.0) samples by using electrochemical method, and performed synchrotron x-ray diffraction, Cu K-edge x-ray absorption fine structure (XAFS), and magnetic susceptibility measurements. With increasing x, a- and c-lattice parameters monotonically increase, which shows lithium intercalation into Bi2Sr2CaCu2O8+δ. Accompanied by the lithium insertion, the valence of Cu ion changes from Cu2+/Cu3+ to Cu1+/Cu2+ to realize charge neutrality. This change of the valence was detected by Cu K-edge XAFS measurement. A clear increase of spectral weight that corresponds to 1s→ 4pπ(3d10L) was observed at around 8982 eV with x. The superconducting (SC) transition temperature TC significantly changes from 74 K for x = 0 to 90 K for x = 0.8, which is attributed to modified density of states by the decrease of hole concentration. A volume fraction of the superconducting phase was 1-2 % for x >= 0.6 implying phase separation where Li-rich non SC phase and Li-poor SC phase coexist. Such a phase separation is universally seen in electrode active materials.

Linear and circular dichroism characterization of thionine binding mode with DNA polynucleotides

NASA Astrophysics Data System (ADS)

Tuite, Eimer Mary; Nordén, Bengt

2018-01-01

The binding mode of thionine (3,7-diamino-5-phenothiazinium) with alternating and non-alternating DNA polynucleotides at low binding ratios was conclusively determined using linear and circular dichroism spectroscopies. The binding to [poly(dG-dC)]2 and poly(dG)·poly(dC) was purely intercalative and was insensitive to ionic strength. Intercalative binding to [poly(dA-dT)]2 is observed at low ionic strength, but a shift of some dye to an non-intercalative mode is observed as the background salt concentration increases. With poly(dA)·poly(dT), intercalative binding is unfavourable, although some dye molecules may intercalate at low ionic strength, and groove binding is strongly promoted with increasing concentration of background salt. However, stacking with bases is observed with single-stranded poly(dA) and with triplex poly(dT)*poly(dA)·poly(dT) which suggests that the unusual structure of poly(dA)·poly(dT) precludes intercalation. Thionine behaves similarly to the related dye methylene blue, and small differences may be attributed either to the ability of thionine to form H-bonds that stabilize intercalation or to its improved stacking interactions in the basepair pocket on steric grounds.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yilmaz, Ceren; Unal, Ugur; Koc University, Chemistry Department, Rumelifeneri yolu, Sariyer 34450, Istanbul

2012-03-15

In the current study, influence of sodium dodecyl sulfate (SDS) on the crystallization of Zn-Al layered double hydroxide (LDH) was investigated. Depending on the SDS concentration coral-like and for the first time ring-like morphologies were obtained in a urea-hydrolysis method. It was revealed that the surfactant level in the starting solution plays an important role in the morphology. Concentration of surfactant equal to or above the anion exchange capacity of the LDH is influential in creating different morphologies. Another important parameter was the critical micelle concentration (CMC) of the surfactant. Surfactant concentrations well above CMC value resulted in ring-like structures.more » The crystallization mechanism was discussed. - Graphical abstract: Dependence of ZnAl LDH Morphology on SDS concentration. Highlights: Black-Right-Pointing-Pointer In-situ intercalation of SDS in ZnAl LDH was achieved via urea hydrolysis method. Black-Right-Pointing-Pointer Morphology of ZnAl LDH intercalated with SDS depended on the SDS concentration. Black-Right-Pointing-Pointer Ring like morphology for SDS intercalated ZnAl LDH was obtained for the first time. Black-Right-Pointing-Pointer Growth mechanism was discussed. Black-Right-Pointing-Pointer Template assisted growth of ZnAl LDH was proposed.« less

Photocatalytic and adsorption properties of TiO2-pillared montmorillonite obtained by hydrothermally activated intercalation of titanium polyhydroxo complexes

PubMed Central

Ovchinnikov, Nikolay L; Karasev, Nikita S; Kochkina, Nataliya E; Agafonov, Alexander V; Vinogradov, Alexandr V

2018-01-01

We report on a new approach for the synthesis of TiO2-pillared montmorillonite, where the pillars exhibit a high degree of crystallinity (nanocrystals) representing a mixture of anatase and rutile phases. The structures exhibit improved adsorption and photocatalytic activity as a result of hydrothermally activated intercalation of titanium polyhydroxo complexes (i.e., TiCl4 hydrolysis products) in a solution with a concentration close to the sol formation limit. The materials, produced at various annealing temperatures from the intercalated samples, were characterized by infrared spectroscopy, differential scanning calorimetry (DSC)/thermogravimetric analysis (TGA), X-ray diffraction, dynamic light scattering (DLS) measurements, and liquefied nitrogen adsorption/desorption. The photocatalytic activity of the TiO2-pillared materials was studied using the degradation of anionic (methyl orange, MO) and cationic (rhodamine B, RhB) dyes in water under UV irradiation. The combined effect of adsorption and photocatalysis resulted in removal of 100% MO and 97.5% RhB (with an initial concentration of 40 mg/L and a photocatalyst-sorbent concentration of 1 g/L) in about 100 minutes. The produced TiO2-pillared montmorillonite showed increased photocatalytic activity as compared to the commercially available photocatalyst Degussa P25. PMID:29515950

Accomplishment of highly porous-lithium lanthanum titanate through microwave treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lakshmi, D.; Nalini, B., E-mail: jyothsnalalin99@gmail.com; Abhilash, K. P.

Perovskite structured (ABO{sub 3}) lithium lanthanum titanate (LLTO) is a successful electrolyte reported by several scientists in the recent past. It is believed that intercalation and de-intercalation of Li ions inside solid electrolyte can be improved by increasing the porosity of the material. Hence in this research work, an attempt is made to increase the porosity of the LLTO electrolyte by rapid-microwave synthesis route. The microwave prepared LLTO is compared with the sol-gel synthesized LLTO. The prepared samples are analyzed with XRD, SEM, PL and cyclic Voltammetry studies. Morphological analysis proves that microwave synthesized LLTO contains much pores compared tomore » the Sol-gel LLTO. A remarkable difference in its electrochemical property is also demonstrated and analysed with cyclic voltammetric studies and the results are presented.« less

A new cathode material for super-valent battery based on aluminium ion intercalation and deintercalation

PubMed Central

Wang, Wei; Jiang, Bo; Xiong, Weiyi; Sun, He; Lin, Zheshuai; Hu, Liwen; Tu, Jiguo; Hou, Jungang; Zhu, Hongmin; Jiao, Shuqiang

2013-01-01

Due to their small footprint and flexible siting, rechargeable batteries are attractive for energy storage systems. A super-valent battery based on aluminium ion intercalation and deintercalation is proposed in this work with VO2 as cathode and high-purity Al foil as anode. First-principles calculations are also employed to theoretically investigate the crystal structure change and the insertion-extraction mechanism of Al ions in the super-valent battery. Long cycle life, low cost and good capacity are achieved in this battery system. At the current density of 50 mAg−1, the discharge capacity remains 116 mAhg−1 after 100 cycles. Comparing to monovalent Li-ion battery, the super-valent battery has the potential to deliver more charges and gain higher specific capacity. PMID:24287676

Correlating Lithium Hydroxyl Accumulation with Capacity Retention in V2O5 Aerogel Cathodes.

PubMed

Wangoh, Linda W; Huang, Yiqing; Jezorek, Ryan L; Kehoe, Aoife B; Watson, Graeme W; Omenya, Fredrick; Quackenbush, Nicholas F; Chernova, Natasha A; Whittingham, M Stanley; Piper, Louis F J

2016-05-11

V2O5 aerogels are capable of reversibly intercalating more than 5 Li(+)/V2O5 but suffer from lifetime issues due to their poor capacity retention upon cycling. We employed a range of material characterization and electrochemical techniques along with atomic pair distribution function, X-ray photoelectron spectroscopy, and density functional theory to determine the origin of the capacity fading in V2O5 aerogel cathodes. In addition to the expected vanadium redox due to intercalation, we observed LiOH species that formed upon discharge and were only partially removed after charging, resulting in an accumulation of electrochemically inactive LiOH over each cycle. Our results indicate that the tightly bound water that is necessary for maintaining the aerogel structure is also inherently responsible for the capacity fade.

Structure of bayerite-based lithium-aluminum layered double hydroxides (LDHs): observation of monoclinic symmetry.

PubMed

Britto, Sylvia; Kamath, P Vishnu

2009-12-21

The double hydroxides of Li with Al, obtained by the imbibition of Li salts into bayerite and gibbsite-Al(OH)(3), are not different polytypes of the same symmetry but actually crystallize in two different symmetries. The bayerite-derived double hydroxides crystallize with monoclinic symmetry, while the gibbsite-derived hydroxides crystallize with hexagonal symmetry. Successive metal hydroxide layers in the bayerite-derived LDHs are translated by the vector ( approximately -1/3, 0, 1) with respect to each other. The exigency of hydrogen bonding drives the intercalated Cl(-) ion to a site with 2-fold coordination, whereas the intercalated water occupies a site with 6-fold coordination having a pseudotrigonal prismatic symmetry. The nonideal nature of the interlayer sites has implications for the observed selectivity of Li-Al LDHs toward anions of different symmetries.

Correlating Lithium Hydroxyl Accumulation with Capacity Retention in V 2 O 5 Aerogel Cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wangoh, Linda W.; Huang, Yiqing; Jezorek, Ryan L.

V 2O 5 aerogels are capable of reversibly intercalating more than 5 Li +/V 2O 5 but suffer from lifetime issues due to their poor capacity retention upon cycling. We employed a range of material characterization and electrochemical techniques along with atomic pair distribution function, X-ray photoelectron spectroscopy, and density functional theory to determine the origin of the capacity fading in V 2O 5 aerogel cathodes. In addition to the expected vanadium redox due to intercalation, we observed LiOH species that formed upon discharge and were only partially removed after charging, resulting in an accumulation of electrochemically inactive LiOH overmore » each cycle. Our results indicate that the tightly bound water that is necessary for maintaining the aerogel structure is also inherently responsible for the capacity fade.« less

Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation

PubMed Central

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

Amorphous Carbon Nanospheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

Amorphous carbon nanosphere used as the anode material for Li-intercalation in Lithium-ion energy storage. This structure was obtained through a thermal annealing process at a temperature of 3000 degree Kelvin, simulated using the LAMMPS molecular dynamics code on the LCRC Fusion resource. Science: Kah Chun Lau and Larry Curtiss Visualization: Aaron Knoll, Mark Hereld and Michael E. Papka

Structural and Kinetic Properties of Graphite Intercalation Compounds

DTIC Science & Technology

1983-04-29

The exfoliation of graphite-FeCl 3NH has been used for making blankets for the extinction of metal fires [12). In addition. exfoliated graphite is...FeCl3-oH3 has been used (Aerotech GCma, 0.5 MHz wideband) equipped with for making blankets for the extinction of metal fires (3). In addition

Nanocomposites prepared from acrylonitrile butadiene rubber and organically modified montmorillonite with vinyl groups

NASA Astrophysics Data System (ADS)

Han, Mijeong; Kim, Hoonjung; Kim, Eunkyoung

2006-01-01

Nanocomposites were prepared from acrylonitrile-butadiene rubber (NBR), vinyl groups containing organically modified montmorillonite and additives, such as zinc oxide, stearic acid, and sulfur. The organically modified montmorillonites used in these nanocomposites were prepared by ion exchange reactions of N,N'-dimethylalkyl-(p-vinylbenzyl)-ammonium chlorides (DAVBAs, alkyl = octyl, dodecyl, and octadecyl) with sodium montmorillonite (Na+-MMT). NBR nanocomposites were obtained by controlling both the mixing and vulcanization conditions, by using a Brabender mixer and hot-press process. X-ray diffraction (XRD) analysis shows that, depending on the amount of montmorillonite that is added, both exfoliated and intercalated nanocomposite structures are formed. The NBR/DAVBA-MMT nanocomposites exhibit much higher mechanical properties (e.g., tensile strength, Young's modulus, 300% modulus, and hardness) as well as gas barrier properties as compared to NBR Na+-MMT or NBR composites generated from modified montmorillonites without vinyl groups. Consistent with the results of XRD, transmission electron microscopy (TEM) reveals that the intercalation and exfoliation structures of the nanocomposites coexist and that the DAVBA-MMT layers are well dispersed in NBR.

Calcium signaling mediates five types of cell morphological changes to form neural rosettes.

PubMed

Hříbková, Hana; Grabiec, Marta; Klemová, Dobromila; Slaninová, Iva; Sun, Yuh-Man

2018-02-12

Neural rosette formation is a critical morphogenetic process during neural development, whereby neural stem cells are enclosed in rosette niches to equipoise proliferation and differentiation. How neural rosettes form and provide a regulatory micro-environment remains to be elucidated. We employed the human embryonic stem cell-based neural rosette system to investigate the structural development and function of neural rosettes. Our study shows that neural rosette formation consists of five types of morphological change: intercalation, constriction, polarization, elongation and lumen formation. Ca 2+ signaling plays a pivotal role in the five steps by regulating the actions of the cytoskeletal complexes, actin, myosin II and tubulin during intercalation, constriction and elongation. These, in turn, control the polarizing elements, ZO-1, PARD3 and β-catenin during polarization and lumen production for neural rosette formation. We further demonstrate that the dismantlement of neural rosettes, mediated by the destruction of cytoskeletal elements, promotes neurogenesis and astrogenesis prematurely, indicating that an intact rosette structure is essential for orderly neural development. © 2018. Published by The Company of Biologists Ltd.

Sanguinarine interacts with chromatin, modulates epigenetic modifications, and transcription in the context of chromatin.

PubMed

Selvi B, Ruthrotha; Pradhan, Suman Kalyan; Shandilya, Jayasha; Das, Chandrima; Sailaja, Badi Sri; Shankar G, Naga; Gadad, Shrikanth S; Reddy, Ashok; Dasgupta, Dipak; Kundu, Tapas K

2009-02-27

DNA-binding anticancer agents cause alteration in chromatin structure and dynamics. We report the dynamic interaction of the DNA intercalator and potential anticancer plant alkaloid, sanguinarine (SGR), with chromatin. Association of SGR with different levels of chromatin structure was enthalpy driven with micromolar dissociation constant. Apart from DNA, it binds with comparable affinity with core histones and induces chromatin aggregation. The dual binding property of SGR leads to inhibition of core histone modifications. Although it potently inhibits H3K9 methylation by G9a in vitro, H3K4 and H3R17 methylation are more profoundly inhibited in cells. SGR inhibits histone acetylation both in vitro and in vivo. It does not affect the in vitro transcription from DNA template but significantly represses acetylation-dependent chromatin transcription. SGR-mediated repression of epigenetic marks and the alteration of chromatin geography (nucleography) also result in the modulation of global gene expression. These data, conclusively, show an anticancer DNA binding intercalator as a modulator of chromatin modifications and transcription in the chromatin context.

A 2D Conductive Organic-Inorganic Hybrid with Extraordinary Volumetric Capacitance at Minimal Swelling.

PubMed

Xiao, Kefeng; Jiang, Donglin; Amal, Rose; Wang, Da-Wei

2018-05-16

Rational design and synthesis of 2D organic-inorganic hybrid materials is important for transformative technological advances for energy storage. Here, a 2D conductive hybrid lamella and its intercalation properties for thin-film supercapacitors are reported. The 2D organic-inorganic hybrid lamella comprises periodically stacked 2D nanosheets with 11.81 Å basal spacing, and is electronically conductive (605 S m -1 ). In contrast to the pre-existing organic-based 2D materials, this material has extremely low gas-permeable porosity (16.5 m 2 g -1 ) in contrast to the high ionic accessibility. All these structural features collectively contribute to the high capacitances up to 732 F cm -3 , combined with small structural swelling at as low as 4.8% and good stability. At a discharge time of 6 s, the thin-film intercalation electrode delivers an energy density of 24 mWh cm -3 , which universally outperforms the surface-dominant capacitive processes in porous carbons. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3D free-standing nitrogen-doped reduced graphene oxide aerogel as anode material for sodium ion batteries with enhanced sodium storage.

PubMed

Zhang, Jiao; Li, Chuanqi; Peng, Zhikun; Liu, Yushan; Zhang, Jianmin; Liu, Zhongyi; Li, Dan

2017-07-07

Sodium ion batteries have drawn extensive attentions for large-scale energy storage to replace lithium ion batteries primarily due to the natural abundance of sodium resource and low cost, but their energy density and electrochemical performance are hindered by the sluggish diffusion kinetics of sodium ion. Herein, free-standing nitrogen-doped graphene aerogel has been fabricated via hydrothermal reaction as the potential anode material for sodium ion batteries. The three dimensional porous network structure of the graphene aerogel provides sufficient interstitial space for sodium ion accommodation, allowing fast and reversible ion intercalation/de-intercalation. The nitrogen doping could introduce defects on the graphene sheets, making the feasible transport of large-sized sodium ion. Benefiting from the effective structure and nitrogen doping, the obtained material demonstrates high reversible capacities, good cycling performance (287.9 mA h g -1 after 200 cycles at a current density of 100 mA g -1 ), especially superior rate capability (151.9 mA h g -1 at a high current density of 5 A g -1 ).

Preparation and structural characterization of zwitterionic surfactant intercalated into NiZn-layered hydroxide salts

NASA Astrophysics Data System (ADS)

Liu, Jiexiang; Wang, Jianlong; Zhang, Xiaoguang; Fang, Binbin; Hu, Pan; Zhao, Xuyang

2015-10-01

Three zwitterionic surfactants, dodecyl dimethyl carboxylbetaine (DCB), dodecyl dimethyl sulfobetaine (DSB) and N-dodecyl-β-aminoprpionate (DAP), intercalated into NiZn-layered hydroxide salts (NZL-DCB, NZL-DSB and NZL-DAP) were synthesized by the coprecipitation method. The effect of surfactant content, pH, temperature and time of hydrothermal treatment on preparation was investigated and discussed. The NZL-DCB, NZL-DSB and NZL-DAP were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry analysis and differential thermal analysis (TGA/DTA). The results showed that basal spacings of NZL-DCB, NZL-DSB and NZL-DAP were around 3.45, 3.68 and 3.94 nm, respectively. DCB, DSB and DAP probably form an overlapped bilayer in the gallery. TGA/DTA data indicated that NZL-DCB, NZL-DSB and NZL-DAP displayed three loss weight stages: loss of adsorbed and structural water, dehydroxylation of matrix and decomposition of nitrate ions, decomposition and combustion of surfactants. Furthermore, chemical analysis data, BET surface area and scanning electron microscopic (SEM) were also measured and analyzed.

Hydroxy double salts intercalated with Mn(II) complexes as potential contrast agents

NASA Astrophysics Data System (ADS)

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.

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

NASA Technical Reports Server (NTRS)

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

Intercalated cell-specific Rh B glycoprotein deletion diminishes renal ammonia excretion response to hypokalemia

PubMed Central

Bishop, Jesse M.; Lee, Hyun-Wook; Handlogten, Mary E.; Han, Ki-Hwan; Verlander, Jill W.

2013-01-01

The ammonia transporter family member, Rh B Glycoprotein (Rhbg), is an ammonia-specific transporter heavily expressed in the kidney and is necessary for the normal increase in ammonia excretion in response to metabolic acidosis. Hypokalemia is a common clinical condition in which there is increased renal ammonia excretion despite the absence of metabolic acidosis. The purpose of this study was to examine Rhbg's role in this response through the use of mice with intercalated cell-specific Rhbg deletion (IC-Rhbg-KO). Hypokalemia induced by feeding a K+-free diet increased urinary ammonia excretion significantly. In mice with intact Rhbg expression, hypokalemia increased Rhbg protein expression in intercalated cells in the cortical collecting duct (CCD) and in the outer medullary collecting duct (OMCD). Deletion of Rhbg from intercalated cells inhibited hypokalemia-induced changes in urinary total ammonia excretion significantly and completely prevented hypokalemia-induced increases in urinary ammonia concentration, but did not alter urinary pH. We conclude that hypokalemia increases Rhbg expression in intercalated cells in the cortex and outer medulla and that intercalated cell Rhbg expression is necessary for the normal increase in renal ammonia excretion in response to hypokalemia. PMID:23220726

A trap potential model investigation of the optical activity induced in dye-DNA intercalation complexes

NASA Astrophysics Data System (ADS)

Kamiya, Mamoru

1988-02-01

The fundamental features of the optical activity induced in dye-DNA intercalation complexes are studied by application of the trap potential model which is useful to evaluate the induced rotational strength without reference to detailed geometrical information about the intercalation complexes. The specific effect of the potential depth upon the induced optical activity is explained in terms of the relative magnitudes of the wave-phase and helix-phase variations in the path of an electron moving on a restricted helical segment just like an exciton trapped around the dye intercalation site. The parallel and perpendicular components of the induced rotational strength well reflect basic properties of the helicity effects about the longitudinal and tangential axes of the DNA helical cylinder. The trap potential model is applied to optimize the potential parameters so as to reproduce the ionic strength effect upon the optical activity induced to proflavine-DNA intercalation complexes. From relationships between the optimized potential parameters and ionic strengths, it is inferred that increase in the ionic strength contributes to the optical activity induced by the nearest-neighbour interaction between intercalated proflavine and DNA base pairs.

Durability of Intercalated Graphite Epoxy Composites in Low Earth Orbit

NASA Technical Reports Server (NTRS)

Gaier, James R.; Davidson, Michelle L.; Shively, Rhonda

1996-01-01

The electrical conductivity of graphite epoxy composites can be substantially increased by intercalating (inserting guest atoms or molecules between the graphene planes) the graphite fibers before composite formation. The resulting high strength, low density, electrically conducting composites have been proposed for EMI shielding in spacecraft. Questions have been raised, however, about their durability in the space environment, especially with respect to outgassing of the intercalates, which are corrosive species such as bromine. To answer those concerns, six samples of bromine intercalated graphite epoxy composites were included in the third Evaluation of Oxygen Interaction with Materials (EOIM-3) experiment flown on the Space Shuttle Discovery (STS-46). Changes in electrical conductivity, optical reflectance, surface texture, and mass loss for SiO2 protected and unprotected samples were measured after being exposed to the LEO environment for 42 hours. SiO2 protected samples showed no degradation, verifying conventional protection strategies are applicable to bromine intercalated composites. The unprotected samples showed that bromine intercalation does not alter the degradation of graphite-epoxy composites. No bromine was detected to have been released by the fibers allaying fears that outgassing could be disruptive to the sensitive electronics the EMI shield is meant to protect.

Characterization of Depleted-Uranium Strength and Damage Behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gray, III, George T.; Chen, Shuh-Rong; Bronkhorst, Curt A.

2012-12-17

The intent of this report is to document the status of our knowledge of the mechanical and damage behavior of Depleted Uranium(DU hereafter). This report briefly summaries the motivation of the experimental and modeling research conducted at Los Alamos National Laboratory(LANL) on DU since the early 1980’s and thereafter the current experimental data quantifying the strength and damage behavior of DU as a function of a number of experimental variables including processing, strain rate, temperature, stress state, and shock prestraining. The effect of shock prestraining on the structure-property response of DU is described and the effect on post-shock mechanical behaviormore » of DU is discussed. The constitutive experimental data utilized to support the derivation of two constitutive strength (plasticity) models, the Preston-Tonks-Wallace (PTW) and Mechanical Threshold Stress (MTS) models, for both annealed and shock prestrained DU are detailed and the Taylor cylinder validation tests and finite-element modeling (FEM) utilized to validate these strength models is discussed. The similarities and differences in the PTW and MTS model descriptions for DU are discussed for both the annealed and shock prestrained conditions. Quasi-static tensile data as a function of triaxial constraint and spallation test data are described. An appendix additionally briefly describes low-pressure equation-of-state data for DU utilized to support the spallation experiments. The constitutive behavior of DU screw/bolt material is presented. The response of DU subjected to dynamic tensile extrusion testing as a function of temperature is also described. This integrated experimental technique is planned to provide an additional validation test in the future. The damage data as a function of triaxiality, tensile and spallation data, is thereafter utilized to support derivation of the Tensile Plasticity (TEPLA) damage model and simulations for comparison to the DU spallation data are presented. Finally, a discussion of future needs in the area of needed DU strength and damage research at LANL is presented to support the development of physically-based predictive strength and damage modeling capability.« less

"The Electric City": Sherbrooke et son paysage hydroelectrique (1880--1930)

NASA Astrophysics Data System (ADS)

Guillemette, Remi

Ce memoire presente l'imbrication des elements hydroelectrique au sein du paysage de la ville de Sherbrooke entre 1880 et 1930. Nous cherchons a comprendre comment les nouveaux elements energetiques s'integrent a celui-ci et comment la population sherbrookoise se represente ces espaces transformes. Comment le paysage hydroelectrique, en tant qu'espace vu et vecu, interagit-il avec la societe sherbrookoise ? A l'interieur de cette problematique generale, nous chercherons a repondre a trois sous-questions. Quelles sont les transformations physiques et materielles engendrees par l'implantation de cette nouvelle technologie hydroelectrique sur le paysage urbain sherbrookois ? Qu'est-ce que les differents groupes valorisent au sein du paysage ? Quel sens prennent ces nouveaux paysages pour les Sherbrookois ? En effet, l'etude du developpement rapide du potentiel hydroelectrique de la riviere Magog nous amene a demontrer que l'exploitation des ressources energetiques a profondement transforme le paysage de Sherbrooke : vastes modifications du trace des cours d'eau, apparition de batiments specifiques a la production energetique, structures de distributions et infrastructures permettant l'illumination de la ville. Nous avancons aussi que differents groupes d'individus ne valorisent pas les memes elements paysagers. Finalement, nous proposons que le regard porte par les citoyens sur le paysage energetique est tributaire de l'usage qu'ils en font. Comme la fonction des elements energetiques paysagers evolue, le regard qu' ils portent vers ces structures se transforme lui aussi. Mots cles: histoire de Sherbrooke, paysage, hydroelectricite, electricite, transformation de l'espace, histoire environnementale

Modification of thermal and electronic properties of bilayer graphene by using slow Na+ ions

NASA Astrophysics Data System (ADS)

Ryu, Mintae; Lee, Paengro; Kim, Jingul; Park, Heemin; Chung, Jinwook

2016-12-01

Bilayer graphene (BLG) has an extensive list of industrial applications in graphene-based nanodevices such as energy storage devices, flexible displays, and thermoelectric devices. By doping slow Na+ ions on Li-intercalated BLG, we find significantly improved thermal and electronic properties of BLG by using angle-resolved photoemission and high-resolution core level spectroscopy (HRCLS) with synchrotron photons. Our HRCLS data reveal that the adsorbed Na+ ions on a BLG produced by Li-intercalation through single layer graphene (SLG) spontaneously intercalate below the BLG, and substitute Li atoms to form Na-Si bonds at the SiC interface while preserving the same phase of BLG. This is in sharp contrast with no intercalation of Na+ ions on SLG though neutral Na atoms intercalate. The Na+-induced BLG is found to be stable upon heating up to T = 400 °C, but returns to SLG when heated at T d = 500 °C. The evolution of the π-bands upon doping the Na+ ions followed by thermal annealing shows that the carrier concentration of the π-band may be artificially controlled without damaging the Dirac nature of the π-electrons. The doubled desorption temperature from that (T d = 250 °C) of the Na-intercalated SLG together with the electronic stability of the Na+-intercalated BLG may find more practical and effective applications in advancing graphene-based thermoelectric devices and anode materials for rechargeable batteries.

Modelling of adsorption and intercalation of hydrogen on/into tungsten disulphide multilayers and multiwall nanotubes.

PubMed

Martínez, José I; Laikhtman, Alex; Moon, Hoi Ri; Zak, Alla; Alonso, Julio A

2018-05-07

Understanding the interaction of hydrogen with layered materials is crucial in the fields of sensors, catalysis, fuel cells and hydrogen storage, among others. Density functional theory, improved by the introduction of van der Waals dispersion forces, provides an efficient and practical workbench to investigate the interaction of molecular and atomic hydrogen with WS 2 multilayers and nanotubes. We find that H 2 physisorbs on the surface of those materials on top of W atoms, while atomic H chemisorbs on top of S atoms. In the case of nanotubes, the chemisorption strength is sensitive to the nanotube diameter. Diffusion of H 2 on the surface of WS 2 encounters quite small activation barriers whose magnitude helps to explain previous and new experimental results for the observed dependence of the hydrogen concentration with temperature. Intercalation of H 2 between adjacent planar WS 2 layers reveals an endothermic character. Intercalating H atoms is energetically favorable, but the intercalation energy does not compensate for the cost of dissociating the molecules. When H 2 molecules are intercalated between the walls of a double wall nanotube, the rigid confinement induces the dissociation of the confined molecules. A remarkable result is that the presence of a full H 2 monolayer adsorbed on top of the first WS 2 layer of a WS 2 multilayer system strongly facilitates the intercalation of H 2 between WS 2 layers underneath. This opens up an additional gate to intercalation processes.

Development of an antimicrobial material based on a nanocomposite cellulose acetate film for active food packaging.

PubMed

Rodríguez, Francisco J; Torres, Alejandra; Peñaloza, Ángela; Sepúlveda, Hugo; Galotto, María J; Guarda, Abel; Bruna, Julio

2014-01-01

Nanocomposites based on biopolymers have been recognised as potential materials for the development of new ecofriendly food packaging. In addition, if these materials incorporate active substances in their structure, the potential applications are much higher. Therefore, this work was oriented to develop nanocomposites with antimicrobial activity based on cellulose acetate (CA), a commercial organoclay Cloisite30B (C30B), thymol (T) as natural antimicrobial component and tri-ethyl citrate (TEC) as plasticiser. Nanocomposites were prepared by a solvent casting method and consisted of 5% (w/w) of C30B, 5% (w/w) of TEC and variable content of T (0%, 0.5% and 2% w/w). To evaluate the effect of C30B into the CA matrix, CA films without this organoclay but with T were also prepared. All nanocomposites showed the intercalation of CA into the organoclay structure; furthermore this intercalation was favoured when 2% (w/w) of T was added to the nanocomposite. In spite of the observed intercalation, the presence of C30B inside the CA matrices increased the opacity of the films significantly. On the other hand, T showed a plasticiser effect on the thermal properties of CA nanocomposites decreasing glass transition, melting temperature and melting enthalpy. The presence of T in CA nanocomposites also allowed the control de Listeria innocua growth when these materials were placed in contact with this Gram-positive bacterium. Interestingly, antimicrobial activity was increased with the presence of C30B. Finally, studies on T release showed that the clay structure inside the CA matrix did not affect its release rate; however, this nanofiller affected the partition coefficient KP/FS which was higher to CA nanocomposites films than in CA films without organoclay. The results obtained in the present study are really promising to be applied in the manufacture of food packaging materials.

Functional copolymer/organo-MMT nanoarchitectures. VI. Synthesis and characterization of novel nanocomposites by interlamellar controlled/living radical copolymerization via preintercalated RAFT-agent/organoclay complexes.

PubMed

Rzayev, Zakir M O; Söylemez, A Ernur

2011-04-01

We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecylamine (ODA)-MMT organoclays, and a radical initiator. The method includes the following stages: (1) synthesis of RAFT intercalated O-MMTs by a physical or chemical interaction of the RAFT agent having two pendant carboxylic groups [S,S-bis(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate] with surface alkyl amines of O-MMT containing tertiary ammonium cation or primary amine groups through strong H-bonding and complexing/amidization reactions, respectively, and (2) utilization of these well-dispersed and intercalated RAFT ... O-MMT complexes and their amide derivatives as new modified RAFT agents in radical-initiated interlamellar controlled/living copolymerization of itaconic acid (IA)-n-butylmethacrylate (BMA) monomer pair. The structure and compositions of the synthesized RAFT ... O-MMT complexes and functional copolymer/O-MMT hybrids were confirmed by FTIR, XRD, thermal (DSC-TGA), SEM and TEM morphology analyses. It was demonstrated that the degree of interaction/exfoliation, morphology and thermal behavior of nanocomposites significantly depended on the type of organoclay and in situ interaction, as well as on the content of flexible butyl-ester linkages as a internal plasticizer. The results of the comparative analysis of the nanocomposites structure-composition-property relations show that the functional copolymer-organoclay hybrids prepared with reactive RAFT ... ODA-MMT complex and containing a combination of partially intercalated and predominantly exfoliated nano-structures exhibit relatively higher thermal stability and fine dispersed morphology. These effects were explained by in situ interfacial chemical reactions through amidization of RAFT with surface alkyl amine of MMT clay in interlamellar copolymerization. This simple and versatile method can be applied to a wide range of functional monomer/comonomer systems and mono- and bifunctional RAFT compounds for preparation new generation of nanomaterials.

Investigation of the complex structure, comparative DNA-binding and DNA cleavage of two water-soluble mono-nuclear lanthanum(III) complexes and cytotoxic activity of chitosan-coated magnetic nanoparticles as drug delivery for the complexes

NASA Astrophysics Data System (ADS)

Asadi, Zahra; Nasrollahi, Neda; Karbalaei-Heidari, Hamidreza; Eigner, Vaclav; Dusek, Michal; Mobaraki, Nabiallah; Pournejati, Roya

2017-05-01

Two water-soluble mono-nuclear macrocyclic lanthanum(III) complexes of 2,6-diformyl-4-methylphenol with 1,3-diamino-2-propanol (C1) or 1,3-propylenediamine (C2) were synthesized and characterized by UV-Vis, FT-IR, 13C and 1H NMR spectroscopy and elemental analysis. C1 complex was structurally characterized by single-crystal X-ray diffraction, which revealed that the complex was mononuclear and ten-coordinated. The coordination sites around lanthanum(III) were occupied with a five-dentate ligand, two bidentate nitrates, and one water molecule. The interaction of complexes with DNA was studied in buffered aqueous solution at pH 7.4. UV-Vis absorption spectroscopy, emission spectroscopy, circular dichroism (CD) and viscometric measurements provided clear evidence of the intercalation mechanism of binding. The obtained intrinsic binding constants (Kb) 9.3 × 103 and 1.2 × 103 M- 1 for C1 and C2, respectively confirmed that C1 is better intercalator than C2. The DNA docking studies suggested that the complexes bind with DNA in a groove binding mode with the binding affinity of C1 > C2. Moreover, agarose gel electrophoresis study of the DNA-complex for both compounds revealed that the C1 intercalation cause ethidium bromide replacement in a competitive manner which confirms the suggested mechanism of binding. Finally, the anticancer experiments for the treated cancerous cell lines with both synthesized compounds show that these hydrophilic molecules need a suitable carrier to pass through the hydrophobic nature of cell membrane efficiently.

Dual nutraceutical nanohybrids of folic acid and calcium containing layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Tae-Hyun; Oh, Jae-Min, E-mail: jaemin.oh@yonsei.ac.kr

2016-01-15

Dual nutraceutical nanohybrids consisting of organic nutrient, folic acid (FA), and mineral nutrient, calcium, were prepared based on layered double hydroxide (LDH) structure. Among various hybridization methods such as coprecipitation, ion exchange, solid phase reaction and exfoliation-reassembly, it was found that exfoliation-reassembly was the most effective in terms of intercalation of FA moiety between Ca-containing LDH layers. X-ray diffraction patterns and infrared spectra indicated that FA molecules were well stabilized in the interlayer space of LDHs through electrostatic interaction. From the atomic force and scanning electron microscopic studies, particle thickness of LDH was determined to be varied with tens, amore » few and again tens of nanometers in pristine, exfoliated and reassembled state, respectively, while preserving particle diameter. The result confirmed layer-by-layer hybrid structure of FA and LDHs was obtained by exfoliation-reassembly. Solid UV–vis spectra showed 2-dimensional molecular arrangement of FA moiety in hybrid, exhibiting slight red shift in n→π* and π→π* transition. The chemical formulae of FA intercalated Ca-containing LDH were determined to Ca{sub 1.30}Al(OH){sub 4.6}FA{sub 0.74}·3.33H{sub 2}O and Ca{sub 1.53}Fe(OH){sub 5.06}FA{sub 2.24}·9.94H{sub 2}O by inductively coupled plasma-atomic emission spectroscopy, high performance liquid chromatography and thermogravimetry, showing high nutraceutical content of FA and Ca. - Highlights: • We successfully intercalated FA molecules into Ca-containing LDHs. • Exfoliation-reassembly was proven to be the most effective. • The interaction between LDH and FA were studied by FT-IR and UV–vis spectra. • Thermal stability of FA were enhanced by electrostatic interaction with LDH layers.« less

Characterization of a hybrid-smectite nanomaterial formed by immobilizing of N-pyridin-2-ylmethylsuccinamic acid onto (3-aminopropyl)triethoxysilane modified smectite and its potentiometric sensor application

NASA Astrophysics Data System (ADS)

Topcu, Cihan; Caglar, Sema; Caglar, Bulent; Coldur, Fatih; Cubuk, Osman; Sarp, Gokhan; Gedik, Kubra; Bozkurt Cirak, Burcu; Tabak, Ahmet

2016-09-01

A novel N-pyridin-2-ylmethylsuccinamic acid-functionalized smectite nanomaterial was synthesized by immobilizing of N-pyridin-2-ylmethylsuccinamic acid through chemical bonding onto (3-aminopropyl)triethoxysilane modified smectite. The structural, thermal, morphological and surface properties of raw, silane-grafted and the N-pyridin-2-ylmethylsuccinamic acid-functionalized smectites were investigated by various characterization techniques. The thermal analysis data showed the presence of peaks in the temperature range from 200 °C to 600 °C due to the presence of physically adsorbed silanes, intercalated silanes, surface grafted silanes and chemically grafted silane molecules between the smectite layers. The powder x-ray diffraction patterns clearly indicated that the aminopropyl molecules also intercalated into the smectite interlayers as bilayer arrangement whereas N-pyridin-2-ylmethylsuccinamic acid molecules were only attached to 3-aminopropyltriethoxysilane molecules on the external surface and edges of clay and they did not intercalate. Fourier transform infrared spectroscopy confirms N-pyridin-2-ylmethylsuccinamic acid molecules bonding through the amide bond between the amine group of aminopropyltriethoxysilane molecules and a carboxylic acid functional group of N-pyridin-2-ylmethylsuccinamic acid molecules. The guest molecules functionalized onto the smectite caused significant alterations in the textural and morphological parameters of the raw smectite. The anchoring of N-pyridin-2-ylmethylsuccinamic acid molecules led to positive electrophoretic mobility values when compared to starting materials. N-pyridin-2-ylmethylsuccinamic acid-functionalized smectite was employed as an electroactive ingredient in the structure of potentiometric PVC-membrane sensor. The sensor exhibited more selective potentiometric response towards chlorate ions compared to the other common anionic species.

Ab initio simulation of changes in geometry, electronic structure, and Gibbs free energy caused by dehydration of hydrotalcites containing Cl⁻ and CO₃²⁻ counteranions.

PubMed

Costa, Deyse G; Rocha, Alexandre B; Souza, Wladmir F; Chiaro, Sandra Shirley X; Leitão, Alexandre A

2011-04-07

This ab initio study was performed to better understand the correlation between intercalated water molecules and layered double hydroxides (LDH), as well as the changes that occur by the dehydration process of Zn-Al hydrotalcite-like compounds containing Cl⁻ and CO₃²⁻ counterions. We have verified that the strong interaction among intercalated water molecules, cointercalated anions, and OH groups from hydroxyl layers is reflected in the thermal stability of these compounds. The Zn(2/3)Al(1/3)(OH)₂Cl(1/3)·2/3H₂O hydrotalcite loses all the intercalated water molecules around 125 °C, while the Zn(2/3)Al(1/3)(OH)₂(CO₃)(1/6)·4/6H₂O compound dehydrates at about 175 °C. These values are in good agreement with experimental data. The interlayer interactions were discussed on the basis of electron density difference analyses. Our calculation shows that the electron density in the interlayer region decreases during the dehydration process, inducing the migration of the Cl⁻ anion and the displacement of the hydroxyl layer from adjacent layers. Changes in these compound structures occur to recover part of the hydrogen bonds broken due to the removal of water molecules. It was observed that the chloride ion had initially a lower Löwdin charge (Cl(-0.43)), which has increased its absolute value (Cl(-0.58)) after the water molecules removal, while the charges on carbonate ions remain invariant, leading to the conclusion that the Cl⁻ anion can be more influenced by the amount of water molecules in the interlayer space than the CO₃²⁻ anion in hydrotalcite-like compounds.

Electrochemical oxygen intercalation into Sr2IrO4

NASA Astrophysics Data System (ADS)

Fruchter, L.; Brouet, V.; Colson, D.; Moussy, J.-B.; Forget, A.; Li, Z. Z.

2018-01-01

Oxygen was electrochemically intercalated into Sr2IrO4 sintered samples, single crystals and a thin film. We estimate the diffusion length to a few μm and the concentration of the intercalated oxygen to δ ≃ 0.01. The latter is thus much smaller than for the cuprate and nickelate parent compounds, for which δ > 0.1 is obtained, which could be a consequence of larger steric effects. The influence of the oxygen doping state on resistivity is small, indicating also a poor charge transfer to the conduction band. It is shown that electrochemical intercalation of oxygen may also contribute to doping, when gating thin films with ionic liquid in the presence of water.

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

NASA Astrophysics Data System (ADS)

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.

Environmentally benign graphite intercalation compound composition for exfoliated graphite, flexible graphite, and nano-scaled graphene platelets

DOEpatents

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.

A comparative study of graphite electrodes using the co-intercalation phenomenon for rechargeable Li, Na and K batteries.

PubMed

Kim, Haegyeom; Yoon, Gabin; Lim, Kyungmi; Kang, Kisuk

2016-10-18

Here, we demonstrate that graphite can serve as a versatile electrode for various rechargeable battery types by reversibly accommodating solvated alkali ions (such as K, Na, and Li) through co-intercalation in its galleries. The co-intercalation of alkali ions is observed to occur via staging reactions. Notably, their insertion behaviors, including their specific capacity, are remarkably similar regardless of the alkali ion species despite the different solubility limits of K, Na, and Li ions in graphite. Nevertheless, the insertion potentials of the solvated alkali ions differ from each other and are observed to be correlated with the interlayer distance in the intercalated graphite gallery.

Intercalating cobalt between graphene and iridium (111): Spatially dependent kinetics from the edges

NASA Astrophysics Data System (ADS)

Vlaic, Sergio; Rougemaille, Nicolas; Kimouche, Amina; Burgos, Benito Santos; Locatelli, Andrea; Coraux, Johann

2017-10-01

Using low-energy electron microscopy, we image in real time the intercalation of a cobalt monolayer between graphene and the (111) surface of iridium. Our measurements reveal that the edges of a graphene flake represent an energy barrier to intercalation. Based on a simple description of the growth kinetics, we estimate this energy barrier and find small, but substantial, local variations. These local variations suggest a possible influence of the graphene orientation with respect to its substrate and of the graphene edge termination on the energy value of the barrier height. Besides, our measurements show that intercalated cobalt is energetically more favorable than cobalt on bare iridium, indicating a surfactant role of graphene.

Methylene blue binding to DNA with alternating AT base sequence: minor groove binding is favored over intercalation.

PubMed

Rohs, Remo; Sklenar, Heinz

2004-04-01

The results presented in this paper on methylene blue (MB) binding to DNA with AT alternating base sequence complement the data obtained in two former modeling studies of MB binding to GC alternating DNA. In the light of the large amount of experimental data for both systems, this theoretical study is focused on a detailed energetic analysis and comparison in order to understand their different behavior. Since experimental high-resolution structures of the complexes are not available, the analysis is based on energy minimized structural models of the complexes in different binding modes. For both sequences, four different intercalation structures and two models for MB binding in the minor and major groove have been proposed. Solvent electrostatic effects were included in the energetic analysis by using electrostatic continuum theory, and the dependence of MB binding on salt concentration was investigated by solving the non-linear Poisson-Boltzmann equation. We find that the relative stability of the different complexes is similar for the two sequences, in agreement with the interpretation of spectroscopic data. Subtle differences, however, are seen in energy decompositions and can be attributed to the change from symmetric 5'-YpR-3' intercalation to minor groove binding with increasing salt concentration, which is experimentally observed for the AT sequence at lower salt concentration than for the GC sequence. According to our results, this difference is due to the significantly lower non-electrostatic energy for the minor groove complex with AT alternating DNA, whereas the slightly lower binding energy to this sequence is caused by a higher deformation energy of DNA. The energetic data are in agreement with the conclusions derived from different spectroscopic studies and can also be structurally interpreted on the basis of the modeled complexes. The simple static modeling technique and the neglect of entropy terms and of non-electrostatic solute-solvent interactions, which are assumed to be nearly constant for the compared complexes of MB with DNA, seem to be justified by the results.

Conformational preferences of DNA following damage by aristolochic acids: Structural and energetic insights into the different mutagenic potential of the ALI and ALII-N(6)-dA adducts.

PubMed

Kathuria, Preetleen; Sharma, Purshotam; Abendong, Minette N; Wetmore, Stacey D

2015-04-21

Aristolochic acids (AAI and AAII), produced by the Aristolochiaceae family of plants, are classified as group I (human) carcinogens by the International Agency for Research on Cancer. These acids are metabolized in cells to yield aristolactams (ALI and ALII, respectively), which further form bulky adducts with the purine nucleobases. Specifically, the adenine lesions are more persistent in cells and have been associated with chronic renal diseases and related carcinogenesis. To understand the structural basis of the nephrotoxicity induced by AAs, the ALI-N(6)-dA and ALII-N(6)-dA lesions are systematically studied using computational methods. Density functional theory calculations indicate that the aristolactam moiety intrinsically prefers a planar conformation with respect to adenine. Nucleoside and nucleotide models suggest that the anti and syn orientations about the glycosidic bond are isoenergetic for both adducts. Molecular dynamics simulations and free energy calculations reveal that the anti base-displaced intercalated conformation is the most stable conformer for both types of AL-N(6)-dA adducted DNA, which agrees with previous experimental work on the ALII-N(6)-dA adduct and thereby validates our approach. Interestingly, this conformer differs from the dominant conformations adopted by other N6-linked adenine lesions, including those derived from polycyclic aromatic hydrocarbons. Furthermore, the second most stable syn base-displaced intercalated conformation lies closer in energy to the anti base-displaced intercalated conformation for ALI-N(6)-dA compared to ALII-N(6)-dA. This indicates that a mixture of conformations may be detectable for ALI-N(6)-dA in DNA. If this enhanced conformational flexibility of double-stranded DNA persists when bound to a lesion-bypass polymerase, this provides a possible structural explanation for the previously observed greater nephrotoxic potential for the ALI versus ALII-N(6)-dA adduct. In addition, the structural characteristics of the preferred conformations of adducted DNA explain the resistance of these adducts to repair and thereby add to our current understanding of the toxicity of AAs within living cells.

In-situ and Ex-situ Observations of Lithium De-intercalation from LiCoO2: Atomic Force Microscopy and Transmission Electron Microscopy Studies

DTIC Science & Technology

2005-06-01

has a layered structure consisting of lithium and cobalt sheets stacked alternatively between oxygen sheets. Li and Co occupy octahedral sites in...cobalt sheets stacked alternatively between ABCABC close-packed oxygen arrays. Li and Co occupy octahedral sites in alternating layers between the oxygen... Co 4.- o 4 Li Figure 1: Crystal structure of LiCoO2. LiCoO2 has a layered structure consisting of lithium and cobalt sheets stacked alternatively

Le role du phytoplancton de petite taille (<20 mum) dans les variations des proprietes optiques des eaux du Saint-Laurent

NASA Astrophysics Data System (ADS)

Mas, Sebastien

Les mesures satellitaires de couleur des oceans sont largement determinees par les proprietes optiques inherentes (IOPs) des eaux de surface. D'autre part, le phytoplancton de petite taille (<20 mum) est le plus souvent dominant dans les oceans, et peut donc etre une source importante de variation des IOPs dans les oceans. Dans ce contexte, le but principal de ce doctorat etait de definir l'impact du phytoplancton (<20 mum) sur les variations des proprietes optiques de l'Estuaire et du Golfe du Saint-Laurent (Canada). Afin d'atteindre cet objectif, il etait necessaire de determiner en milieu controle les facteurs de variabilite des proprietes optiques cellulaires et des IOPs du phytoplancton (<20 mum) des eaux du Saint-Laurent, et d'evaluer la contribution du phytoplancton (<20 mum) aux proprietes optiques totales des eaux du Saint-Laurent. Des experiences en laboratoire ont montre que les variations des proprietes optiques des cellules phytoplanctoniques soumises a un cycle jour-nuit, ainsi qu'a des changements concomitants d'intensite lumineuse, peuvent contribuer significativement a la variabilite des proprietes optiques observee en milieu naturel. D'autres experiences ont, quant a elles, mis en evidence que les variations des proprietes optiques des cellules phytoplanctoniques dues aux phases de croissance peuvent alterer les IOPs des oceans, particulierement pendant les periodes de floraison. De plus, la presence de bacteries et de particules detritiques peut egalement affecter la variabilite des IOPs totales, notamment la diffusion. Au printemps, dans l'Estuaire et le Golfe du Saint-Laurent, la contribution du phytoplancton <20 mum aux IOPs presentait des differences regionales evidentes pour les proprietes d'absorption et de diffusion. En plus de la variabilite spatiale, les proprietes optiques cellulaires presentaient des variations journalieres, et ce particulierement pour le picophytoplancton. Enfin, la plupart des differences observees dans les proprietes biooptiques, particulierement l'absorption, etaient attribuables a la contribution du phytoplancton <20 mum. Ceci confirme l'importance de la structure de taille des communautes phytoplanctoniques dans les modeles bio-optiques appliques au Saint-Laurent. L'ensemble des resultats a permis de mettre en evidence l'importance des mecanismes de photoacclimatation et de synchronisation du cycle cellulaire du phytoplancton sur les variations journalieres des IOPs, ainsi que de l'etat physiologique relie au stade de croissance sur les variations temporelles a long terme des IOPs. De plus, le phytoplancton <20 mum contribue de maniere importante aux IOPs et a leur variabilite dans l'Estuaire et le Golfe du St-Laurent, et ce particulierement pour l'absorption. Cette etude de doctorat souligne donc l'importance du phytoplancton <20 mum sur la variabilite des IOPs des oceans.

Effect of friction on oxidative graphite intercalation and high-quality graphene formation.

PubMed

Seiler, Steffen; Halbig, Christian E; Grote, Fabian; Rietsch, Philipp; Börrnert, Felix; Kaiser, Ute; Meyer, Bernd; Eigler, Siegfried

2018-02-26

Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant.

Iodine Intercalation of Bundles of Single Wall Carbon Nanotubes (SWNT)

NASA Astrophysics Data System (ADS)

Grigorian, L.; Fang, S. L.; Williams, K. A.; Sumanasekera, G. U.; Dickey, E. C.; Eklund, P. C.; Pennycock, S.; Rinzler, A. G.; Smalley, R. E.

1998-03-01

We have been able to intercalate iodine into the interstitial channels within the rope lattice by direct contact of SWNT mats with molten iodine. These continuously filled channels were observed by Z-contrast STEM imaging. The intercalated iodine atoms provide a ``chemical wedge'' which expands the rope lattice as found from x-ray powder diffraction. At low doping level, Raman-active modes and photoluminescence were used to identify the intercalated species as (I_3)^-I2 linear polyiodide chains. The observed upshift of the high-frequency tangential Raman mode, as well as decreased values of four-probe electrical resistance and thermopower are all consistent with electron transfer from SWNT to iodine. At higher doping level, another iodine-SWNT compound was formed as evidenced by a different x-ray diffraction pattern and Raman spectrum. This new compound exhibits a number of new Raman lines, apparently unrelated to the intercalated iodine, in addition to the usual SWNT Raman modes. We discuss possible mechanisms responsible for activating new Raman modes in SWNT.

Intercalated hybrid of kaolinite with KH2PO4 showing high ionic conductivity (∼10-4 S cm-1) at room temperature

NASA Astrophysics Data System (ADS)

Liu, Shao-Xian; Xue, Chen; Yang, Hao; Huang, Xiao-Qing; Zou, Yang; Ding, Yan-Ni; Li, Li; Ren, Xiao-Ming

2017-12-01

In this paper, we present the study of preparation and ionic conductance for an intercalated hybrid of kaolinite with potassium dihydrogen. The intercalation efficiency is high up to ca. 90%. The intercalated hybrid has been characterized by powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The ionic conductivity (σ) of the hybrid material is strongly dependent on the moisture in the environment, with σ = 8.4 × 10-10 S cm-1 at 293 K and gradually increases to 7.16 × 10-9 S cm-1 under N2 atmosphere (anhydrous environment) at 353 K as well as an activation energy of Ea = 0.618 e V, whereas σ = 2.19 × 10-4 S cm-1 at 100% relative humidity and 293 K with Ea = 0.44 eV. The mechanism that the moisture affects the ionic conductance of the intercalated hybrid is further discussed.

Process to Selectively Distinguish Viable from Non-Viable Bacterial Cells

NASA Technical Reports Server (NTRS)

LaDuc, Myron T.; Bernardini, Jame N.; Stam, Christina N.

2010-01-01

The combination of ethidium monoazide (EMA) and post-fragmentation, randomly primed DNA amplification technologies will enhance the analytical capability to discern viable from non-viable bacterial cells in spacecraft-related samples. Intercalating agents have been widely used since the inception of molecular biology to stain and visualize nucleic acids. Only recently, intercalating agents such as EMA have been exploited to selectively distinguish viable from dead bacterial cells. Intercalating dyes can only penetrate the membranes of dead cells. Once through the membrane and actually inside the cell, they intercalate DNA and, upon photolysis with visible light, produce stable DNA monoadducts. Once the DNA is crosslinked, it becomes insoluble and unable to be fragmented for post-fragmentation, randomly primed DNA library formation. Viable organisms DNA remains unaffected by the intercalating agents, allowing for amplification via post-fragmentation, randomly primed technologies. This results in the ability to carry out downstream nucleic acid-based analyses on viable microbes to the exclusion of all non-viable cells.

Electrochemical and in-situ X-ray diffraction studies of Ti 3C 2T x MXene in ionic liquid electrolyte

DOE PAGES

Lin, Zifeng; Rozier, Patrick; Duployer, Benjamin; ...

2016-08-26

2D titanium carbide (Ti 3C 2T x MXene) showed good capacitance in both organic and neat ionic liquid electrolytes, but its charge storage mechanism is still not fully understood. Here, electrochemical characteristics of Ti 3C 2T x electrode were studied in neat EMI-TFSI electrolyte. A capacitive behavior was observed within a large electrochemical potential range (from – 1.5 to 1.5 V vs. Ag). Intercalation and de-intercalation of EMI + cations and/or TFSI– anions were investigated by in-situ X-ray diffraction. Interlayer spacing of Ti 3C 2T x flakes decreases during positive polarization, which can be ascribed to either electrostatic attraction effectmore » between intercalated TFSI– anions and positively charged Ti 3C 2T x nanosheets or steric effect caused by de-intercalation of EMI + cations. In conclusion, the expansion of interlayer spacing when polarized to negative potentials is explained by steric effect of cation intercalation.« less

Thermodynamics, Kinetics and Structural Evolution of ε-LiVOPO 4 over Multiple Lithium Intercalation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yuh-Chieh; Wen, Bohua; Wiaderek, Kamila M.

In this work, we demonstrate the stable cycling of more than one Li in solid-state-synthesized ε-LiVOPO4 over more than 20 cycles for the first time. Using a combination of density functional theory (DFT) calculations, X-ray pair distribution function (PDF) analysis and X-ray absorption near edge structure (XANES) measurements, we present a comprehensive analysis of the thermodynamics, kinetics, and structural evolution of ε-LixVOPO4 over the entire lithiation range. We identify two intermediate phases at x = 1.5 and 1.75 in the low-voltage regime using DFT calculations, and the computed and electrochemical voltage profiles are in excellent agreement. Operando PDF and EXAFSmore » techniques show a reversible hysteretic change in the short (<2 Å) V—O bond lengths coupled with an irreversible extension of the long V—O bond (>2.4 Å) during low-voltage cycling. Hydrogen intercalation from electrolyte decomposition is a possible explanation for the ~2.4 Å V—O bond and its irreversible extension. Finally, we show that ε-LixVOPO4 is likely a pseudo-1D ionic diffuser with low electronic conductivity using DFT calculations, which suggests that nanosizing and carbon coating is necessary to achieve good electrochemical performance in this material.« less

Open-Structured V 2 O 5 · n H 2 O Nanoflakes as Highly Reversible Cathode Material for Monovalent and Multivalent Intercalation Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Huali; Bi, Xuanxuan; Bai, Ying

The high-capacity cathode material V2O5·nH2O has attracted considerable attention for metal ion batteries due to the multielectron redox reaction during electrochemical processes. It has an expanded layer structure, which can host large ions or multivalent ions. However, structural instability and poor electronic and ionic conductivities greatly handicap its application. Here, in cell tests, self-assembly V2O5·nH2O nanoflakes shows excellent electrochemical performance with either monovalent or multivalent cation intercalation. They are directly grown on a 3D conductive stainless steel mesh substrate via a simple and green hydrothermal method. Well-layered nanoflakes are obtained after heat treatment at 300 °C (V2O5·0.3H2O). Nanoflakes with ultrathinmore » flower petals deliver a stable capacity of 250 mA h g-1 in a Li-ion cell, 110 mA h g-1 in a Na-ion cell, and 80 mA h g-1 in an Al-ion cell in their respective potential ranges (2.0–4.0 V for Li and Na-ion batteries and 0.1–2.5 V for Al-ion battery) after 100 cycles.« less

Probing the thermal stability and the decomposition mechanism of a magnesium-fullerene polymer via X-ray Raman spectroscopy, X-ray diffraction and molecular dynamics simulations.

PubMed

Aramini, Matteo; Niskanen, Johannes; Cavallari, Chiara; Pontiroli, Daniele; Musazay, Abdurrahman; Krisch, Michael; Hakala, Mikko; Huotari, Simo

2016-02-21

We report the microscopic view of the thermal structural stability of the magnesium intercalated fullerene polymer Mg2C60. With the application of X-ray Raman spectroscopy and X-ray diffraction, we study in detail the decomposition pathways of the polymer system upon annealing at temperatures between 300 and 700 °C. We show that there are at least two energy scales involved in the decomposition reaction. Intermolecular carbon bonds, which are responsible for the formation of a 2D fullerene polymer, are broken with a relatively modest thermal energy, while the long-range order of the original polymer remains intact. With an increased thermal energy, the crystal structure in turn is found to undergo a transition to a novel intercalated cubic phase that is stable up to the highest temperature studied here. The local structure surrounding magnesium ions gets severely modified close to, possibly at, the phase transition. We used density functional theory based calculations to study the thermodynamic and kinetic aspects of the collapse of the fullerene network, and to explain the intermediate steps as well as the reaction pathways in the break-up of this peculiar C60 intermolecular bonding architecture.

Fluorescence and confocal imaging of mammalian cells using conjugated oligoelectrolytes with phenylenevinylene core

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milczarek, Justyna; Pawlowska, Roza; Zurawinski, Remigiusz

Over the last few years, considerable efforts are taken, in order to find a molecular fluorescent probe fulfilling their applicability requirements. Due to a good optical properties and affinity to biological structures conjugated oligoelectrolytes (COEs) can be considered as a promising dyes for application in fluorescence-based bioimaging. In this work, we synthetized COEs with phenylenevinylene core (PV-COEs) and applied as fluorescent membranous-specific probes. Cytotoxicity effects of each COE were probed on cancerous and non-cancerous cell types and little to no toxicity effects were observed at the high range of concentrations. The intensity of cell fluorescence following the COE staining wasmore » determined by the photoluminescence analysis and fluorescence activated cell sorting method (FACS). Intercalation of tested COEs into mammalian cell membranes was revealed by fluorescent and confocal microscopy colocalization with commercial dyes specific for cellular structures including mitochondria, Golgi apparatus and endoplasmic reticulum. The phenylenevinylene conjugated oligoelectrolytes have been found to be suitable for fluorescent bioimaging of mammalian cells and membrane-rich organelles. Due to their water solubility coupled with spontaneous intercalation into cells, favorable photophysical features, ease of cell staining, low cytotoxicity and selectivity for membranous structures, PV-COEs can be applied as markers for fluorescence imaging of a variety of cell types.« less

Spectroscopic and thermodynamic insights into the interaction between proflavine and human telomeric G-quadruplex DNA.

PubMed

Kumar, Vivek; Sengupta, Abhigyan; Gavvala, Krishna; Koninti, Raj Kumar; Hazra, Partha

2014-09-25

The G-quadruplex (GQ-DNA), an alternative structure motif of DNA, has emerged as a novel and exciting target for anticancer drug discovery. GQ-DNA formed in the presence of monovalent cations (Na(+)/K(+)) by human telomeric DNA is a point of interest due to their direct relevance for cellular aging and abnormal cell growths. Small molecules that selectively target and stabilize G-quadruplex structures are considered to be potential therapeutic anticancer agents. Herein, we probe G-quadruplex and proflavine (a well-known DNA intercalator, hence acting as an anticarcinogen) association through steady state and time-resolved fluorescence spectroscopy to explore the effect of stabilization of GQ-DNA by this well-known DNA intercalator. The structural modifications of G-quadruplex upon binding are highlighted through circular dichroism (CD) spectra. Moreover, a detailed insight into the thermodynamics of this interaction has been provided though isothermal titration calorimetry (ITC) studies. The thermodynamic parameters obtained from ITC help to gain knowledge about the nature as well as the driving forces of binding. This present study shows that proflavine (PF) can act as a stabilizer of telomeric GQ-DNA through an entropically as well as enthalpically feasible process with high binding affinity and thereby can be considered as a potential telomerase inhibitor.

The electrochemical performance of super P carbon black in reversible Li/Na ion uptake

NASA Astrophysics Data System (ADS)

Peng, Bo; Xu, Yaolin; Wang, Xiaoqun; Shi, Xinghua; Mulder, Fokko M.

2017-06-01

Super P carbon black (SPCB) has been widely used as a conducting additive in Li/Na ion batteries to improve the electronic conductivity. However, there has not yet been a comprehensive study on its structure and electrochemical properties for Li/Na ion uptake, though it is important to characterize its contribution in any study of active materials that uses this additive in non-negligible amounts. In this article the structure of SPCB has been characterized and a comprehensive study on the electrochemical Li/Na ion uptake capability and reaction mechanisms are reported. SPCB exhibits a considerable lithiation capacity (up to 310 mAh g-1) from the Li ion intercalation in the graphite structure. Sodiation in SPCB undergoes two stages: Na ion intercalation into the layers between the graphene sheets and the Na plating in the pores between the nano-graphitic domains, and a sodiation capacity up to 145 mAh g-1 has been achieved. Moreover, the influence of the type and content of binders on the lithiation and sodiation properties has been investigated. The cycling stability is much enhanced with sodium carboxymethyl cellulose (NaCMC) binder in the electrode and fluoroethylene carbonate (FEC) in the electrolyte; and a higher content of binder improves the Coulombic efficiency during dis-/charge.

Electronic properties of carbon fibers intercalated with copper chloride

NASA Technical Reports Server (NTRS)

Oshima, H.; Natarajan, V.; Woollam, J. A.; Yavrouian, A.; Haugland, E. J.; Tsuzuku, T.

1984-01-01

Copper chloride intercalated pitch-based carbon fibers are found to have electrical resistivities as low as 12.9 micro-ohm-cm, and are air- and thermally-stable at and above room temperature. This is therefore a good candidate system for conductor application. In addition, Shubnikov-deHaas quantum oscillatory effects were found, and electronic properties of the intercalated fiber are studied using magnetic fields to 20 tesla.

Kaolinite Nanocomposite Platelets Synthesized by Intercalation and Imidization of Poly(styrene-co-maleic anhydride)

PubMed Central

Samyn, Pieter; Schoukens, Gustaaf; Stanssens, Dirk

2015-01-01

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. PMID:28793445

Self-Activating, Capacitive Anion Intercalation Enables High-Power Graphite Cathodes.

PubMed

Wang, Gang; Yu, Minghao; Wang, Jungang; Li, Debao; Tan, Deming; Löffler, Markus; Zhuang, Xiaodong; Müllen, Klaus; Feng, Xinliang

2018-05-01

Developing high-power cathodes is crucial to construct next-generation quick-charge batteries for electric transportation and grid applications. However, this mainly relies on nanoengineering strategies at the expense of low scalability and high battery cost. Another option is provided herein to build high-power cathodes by exploiting inexpensive bulk graphite as the active electrode material, where anion intercalation is involved. With the assistance of a strong alginate binder, the disintegration problem of graphite cathodes due to the large volume variation of >130% is well suppressed, making it possible to investigate the intrinsic electrochemical behavior and to elucidate the charge storage kinetics of graphite cathodes. Ultrahigh power capability up to 42.9 kW kg -1 at the energy density of >300 Wh kg -1 (based on graphite mass) and long cycling life over 10 000 cycles are achieved, much higher than those of conventional cathode materials for Li-ion batteries. A self-activating and capacitive anion intercalation into graphite is discovered for the first time, making graphite a new intrinsic intercalation-pseudocapacitance cathode material. The finding highlights the kinetical difference of anion intercalation (as cathode) from cation intercalation (as anode) into graphitic carbon materials, and new high-power energy storage devices will be inspired. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stochasticity and stereotypy in the Ciona notochord.

PubMed

Carlson, Maia; Reeves, Wendy; Veeman, Michael

2015-01-15

Fate mapping with single cell resolution has typically been confined to embryos with completely stereotyped development. The lineages giving rise to the 40 cells of the Ciona notochord are invariant, but the intercalation of those cells into a single-file column is not. Here we use genetic labeling methods to fate map the Ciona notochord with both high resolution and large sample sizes. We find that the ordering of notochord cells into a single column is not random, but instead shows a distinctive signature characteristic of mediolaterally-biased intercalation. We find that patterns of cell intercalation in the notochord are somewhat stochastic but far more stereotyped than previously believed. Cell behaviors vary by lineage, with the secondary notochord lineage being much more constrained than the primary lineage. Within the primary lineage, patterns of intercalation reflect the geometry of the intercalating tissue. We identify the latest point at which notochord morphogenesis is largely stereotyped, which is shortly before the onset of mediolateral intercalation and immediately after the final cell divisions in the primary lineage. These divisions are consistently oriented along the AP axis. Our results indicate that the interplay between stereotyped and stochastic cell behaviors in morphogenesis can only be assessed by fate mapping experiments that have both cellular resolution and large sample sizes. Copyright © 2014 Elsevier Inc. All rights reserved.

Stochasticity and Stereotypy in the Ciona Notochord

PubMed Central

Carlson, Maia; Reeves, Wendy; Veeman, Michael

2015-01-01

Fate mapping with single cell resolution has typically been confined to embryos with completely stereotyped development. The lineages giving rise to the 40 cells of the Ciona notochord are invariant, but the intercalation of those cells into a single-file column is not. Here we use genetic labeling methods to fate map the Ciona notochord with both high resolution and large sample sizes. We find that the ordering of notochord cells into a single column is not random, but instead shows a distinctive signature characteristic of mediolaterally-biased intercalation. We find that patterns of cell intercalation in the notochord are somewhat stochastic but far more stereotyped than previously believed. Cell behaviors vary by lineage, with the secondary notochord lineage being much more constrained than the primary lineage. Within the primary lineage, patterns of intercalation reflect the geometry of the intercalating tissue. We identify the latest point at which notochord morphogenesis is largely stereotyped, which is shortly before the onset of mediolateral intercalation and immediately after the final cell divisions in the primary lineage. These divisions are consistently oriented along the AP axis. Our results indicate that the interplay between stereotyped and stochastic cell behaviors in morphogenesis can only be assessed by fate mapping experiments that have both cellular resolution and large sample sizes. PMID:25459659

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

PubMed

Abdul Latip, Ahmad Faiz; Hussein, Mohd Zobir; Stanslas, Johnson; Wong, Charng Choon; Adnan, Rohana

2013-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2004-12-01

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

Synthesis, structural, thermal and optical studies of inorganic-organic hybrid semiconductors, R-PbI4

NASA Astrophysics Data System (ADS)

Pradeesh, K.; Nageswara Rao, K.; Vijaya Prakash, G.

2013-02-01

Wide varieties of naturally self-assembled two-dimensional inorganic-organic (IO) hybrid semiconductors, (4-ClC6H4NH3)2PbI4, (C6H9C2H4NH3)2PbI4, (CnH2n+1NH3)2PbI4 (where n = 12, 16, 18), (CnH2n-1NH3)2PbI4 (where n = 3, 4, 5), (C6H5C2H4NH3)2PbI4, NH3(CH2)12NH3PbI4, and (C4H3SC2H4NH3)2PbI4, were fabricated by intercalating structurally diverse organic guest moieties into lead iodide perovskite structure. The crystal packing of all these fabricated IO-hybrids comprises of well-ordered organic and inorganic layers, stacked-up alternately along c-axis. Almost all these hybrids are thermally stable upto 200 °C and show strong room-temperature exciton absorption and photoluminescence features. These strongly confined optical excitons are highly influenced by structural deformation of PbI matrix due to the conformation of organic moiety. A systematic correlation of optical exciton behavior of IO-hybrids with the organic/inorganic layer thicknesses, intercalating organic moieties, and various structural disorders were discussed. This systematic study clearly suggests that the PbI layer crumpling is directly responsible for the tunability of optical exciton energy.

Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

PubMed

He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

2016-06-08

Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability.

Control of crystallite and particle size in the synthesis of layered double hydroxides: Macromolecular insights and a complementary modeling tool.

PubMed

Galvão, Tiago L P; Neves, Cristina S; Caetano, Ana P F; Maia, Frederico; Mata, Diogo; Malheiro, Eliana; Ferreira, Maria J; Bastos, Alexandre C; Salak, Andrei N; Gomes, José R B; Tedim, João; Ferreira, Mário G S

2016-04-15

Zinc-aluminum layered double hydroxides with nitrate intercalated (Zn(n)Al-NO3, n=Zn/Al) is an intermediate material for the intercalation of different functional molecules used in a wide range of industrial applications. The synthesis of Zn(2)Al-NO3 was investigated considering the time and temperature of hydrothermal treatment. By examining the crystallite size in two different directions, hydrodynamic particle size, morphology, crystal structure and chemical species in solution, it was possible to understand the crystallization and dissolution processes involved in the mechanisms of crystallite and particle growth. In addition, hydrogeochemical modeling rendered insights on the speciation of different metal cations in solution. Therefore, this tool can be a promising solution to model and optimize the synthesis of layered double hydroxide-based materials for industrial applications. Copyright © 2016 Elsevier Inc. All rights reserved.

The effect of cation doping on spinel LiMn 2O 4: a first-principles investigation

NASA Astrophysics Data System (ADS)

Shi, Siqi; Ouyang, Chuying; Wang, Ding-sheng; Chen, Liquan; Huang, Xuejie

2003-05-01

The effect of the cation doping on the electronic structure of spinel LiM yMn 2- yO 4 (M=Cr, Mn, Fe, Co and Ni) has been calculated by first-principles. Our calculation shows that new M-3d bands emerge in the density of states compared with that in LiMn 2O 4. Simultaneously, the new O-2p bands appear accordingly in almost the same energy range around the Fermi energy owing to the M-3d/O-2p interaction. It is found that the appearance of new O-2p bands in the lower energy position results in a higher intercalation voltage. Consequently, the origin of higher intercalation voltage in LiM yMn 2- yO 4 can be ascribed to the lower O-2p level introduced by the doping cation M.

Polymer Layered Silicate Nanocomposites: A Review

PubMed Central

Mittal, Vikas

2009-01-01

This review aims to present recent advances in the synthesis and structure characterization as well as the properties of polymer layered silicate nanocomposites. The advent of polymer layered silicate nanocomposites has revolutionized research into polymer composite materials. Nanocomposites are organic-inorganic hybrid materials in which at least one dimension of the filler is less than 100 nm. A number of synthesis routes have been developed in the recent years to prepare these materials, which include intercalation of polymers or pre-polymers from solution, in-situ polymerization, melt intercalation etc. The nanocomposites where the filler platelets can be dispersed in the polymer at the nanometer scale owing to the specific filler surface modifications, exhibit significant improvement in the composite properties, which include enhanced mechanical strength, gas barrier, thermal stability, flame retardancy etc. Only a small amount of filler is generally required for the enhancement in the properties, which helps the composite materials retain transparency and low density.

Gaussian approximation potential modeling of lithium intercalation in carbon nanostructures

NASA Astrophysics Data System (ADS)

Fujikake, So; Deringer, Volker L.; Lee, Tae Hoon; Krynski, Marcin; Elliott, Stephen R.; Csányi, Gábor

2018-06-01

We demonstrate how machine-learning based interatomic potentials can be used to model guest atoms in host structures. Specifically, we generate Gaussian approximation potential (GAP) models for the interaction of lithium atoms with graphene, graphite, and disordered carbon nanostructures, based on reference density functional theory data. Rather than treating the full Li-C system, we demonstrate how the energy and force differences arising from Li intercalation can be modeled and then added to a (prexisting and unmodified) GAP model of pure elemental carbon. Furthermore, we show the benefit of using an explicit pair potential fit to capture "effective" Li-Li interactions and to improve the performance of the GAP model. This provides proof-of-concept for modeling guest atoms in host frameworks with machine-learning based potentials and in the longer run is promising for carrying out detailed atomistic studies of battery materials.

Rocking-Chair Configuration in Ultrathin Lithium Vanadate-Graphene Hybrid Nanosheets for Electrical Modulation

PubMed Central

Zhu, Haiou; Qin, Xinming; Sun, Xu; Yan, Wensheng; Yang, Jinlong; Xie, Yi

2013-01-01

The ability to control electronic property of a material by externally applied voltage is greatly anticipated in modern electronics, and graphene provide potential application foreground for this issue on account of its exotic ambipolar transport property. In this study, we proposed that inorganic-graphene intercalated nanosheet is an effective solution to optimize the transport property of graphene. As an example, lithium vanadate-graphene (LiVO-graphene) alternately intercalated nanosheets were designed and successfully synthesized. Theoretical calculation implied that its rocking chair configuration may provide a new pathway to switch the carrier in graphene layer between p-type and n-type while the position of embedded Li ions is controlled by an external field. Thus, a demo transistor was fabricated with layer-by-layer overlapping of LiVO-graphene nanosheets which proved that this inorganic-graphene structure could be used for electrical modulation in electronic devices. PMID:23409237

Atomic force microscopy studies on molybdenum disulfide flakes as sodium-ion anodes.

PubMed

Lacey, Steven D; Wan, Jiayu; von Wald Cresce, Arthur; Russell, Selena M; Dai, Jiaqi; Bao, Wenzhong; Xu, Kang; Hu, Liangbing

2015-02-11

A microscale battery comprised of mechanically exfoliated molybdenum disulfide (MoS2) flakes with copper connections and a sodium metal reference was created and investigated as an intercalation model using in situ atomic force microscopy in a dry room environment. While an ethylene carbonate-based electrolyte with a low vapor pressure allowed topographical observations in an open cell configuration, the planar microbattery was used to conduct in situ measurements to understand the structural changes and the concomitant solid electrolyte interphase (SEI) formation at the nanoscale. Topographical observations demonstrated permanent wrinkling behavior of MoS2 electrodes upon sodiation at 0.4 V. SEI formation occurred quickly on both flake edges and planes at voltages before sodium intercalation. Force spectroscopy measurements provided quantitative data on the SEI thickness for MoS2 electrodes in sodium-ion batteries for the first time.

Preparation and properties of poly HTBN-based urethane-urea/organo reactive montmorillonite nanocomposites

NASA Astrophysics Data System (ADS)

Li, Zai-Feng; Wu, Yuan; Zhang, Fu-Tao; Cao, Yu-Yang; Wu, Shou-Peng; Wang, Ting

2012-12-01

With ultrasonic assistant mixing way, an intercalated mixture of polyol/organo reactive montmorillonite (ORMMT) was pretreated. The prepolymer composed MMT clay was prepared by reaction of polyol/ORMMT mixture with toluene diisocyanate (TDI). The resultant prepolymer reacted with extender (DMTDA) and then the polyurethane-urea/organo reactive montmorillonite (PUU/ORMMT) nanocomposites were obtained. The structure, morphology and properties of PUU/ORMMT nanocomposites were characterized by FT-IR, TEM, AFM, strain-stress machine, TGA, and dynamic mechanical analysis (DMA). The results showed that when the OMMT content is 3%, the PUU/ORMMT nanocomposities performed super mechanical properties. Because of the presence of ORMMT, both T g of the soft segment and tan δ of the PUU increased, and the decomposition temperature for the first step and the second step increased respectively. TEM images showed that the organophilic MMT particles in the PUU composite exhibit a high degree of intercalation and exfoliation.

Synthesis and electrochemical properties of niobium pentoxide deposited on layered carbide-derived carbon

NASA Astrophysics Data System (ADS)

Zhang, Chuanfang (John); Maloney, Ryan; Lukatskaya, Maria R.; Beidaghi, Majid; Dyatkin, Boris; Perre, Emilie; Long, Donghui; Qiao, Wenming; Dunn, Bruce; Gogotsi, Yury

2015-01-01

Herein we report on the hydrothermal synthesis of niobium pentoxide on carbide-derived carbon (Nb2O5/CDC) with a layered structure. The presence of phenylphosphonic acid guides the deposition during preparation, leading to the formation of amorphous Nb2O5 particles which are 4-10 nm in diameter and homogeneously distributed on the CDC framework. Electrochemical testing of the Nb2O5/CDC electrode indicated that the highest capacitance and Coulombic efficiency occurred using an electrolyte comprised of 1 M lithium perchlorate in ethylene carbonate/dimethyl carbonate. Subsequent heat treatment of Nb2O5/CDC in CO2 environment led to crystallization of the Nb2O5, allowing reversible Li+ intercalation/de-intercalation. For sweep rates corresponding to charging and discharging in under 3 min, a volumetric charge of 180 C cm-3 and Coulombic efficiency of 99.2% were attained.

Convergence and Extrusion Are Required for Normal Fusion of the Mammalian Secondary Palate

PubMed Central

Kim, Seungil; Lewis, Ace E.; Singh, Vivek; Ma, Xuefei; Adelstein, Robert; Bush, Jeffrey O.

2015-01-01

The fusion of two distinct prominences into one continuous structure is common during development and typically requires integration of two epithelia and subsequent removal of that intervening epithelium. Using confocal live imaging, we directly observed the cellular processes underlying tissue fusion, using the secondary palatal shelves as a model. We find that convergence of a multi-layered epithelium into a single-layer epithelium is an essential early step, driven by cell intercalation, and is concurrent to orthogonal cell displacement and epithelial cell extrusion. Functional studies in mice indicate that this process requires an actomyosin contractility pathway involving Rho kinase (ROCK) and myosin light chain kinase (MLCK), culminating in the activation of non-muscle myosin IIA (NMIIA). Together, these data indicate that actomyosin contractility drives cell intercalation and cell extrusion during palate fusion and suggest a general mechanism for tissue fusion in development. PMID:25848986

Optical and Thermal Behaviors of Polyamide-Layered Silicate Nanocomposites Based on 4,4'-Azodibenzoic Acid by Solution Intercalation Technique

NASA Astrophysics Data System (ADS)

Faghihi, Khalil; Shabanian, Meisam

2011-04-01

Two new samples of polyamide-montmorillonite reinforced nanocomposites based on 4,4'-azodibenzoic acid were prepared by a convenient solution intercalation technique. Polyamide (PA) 4 as a source of polymer matrix was synthesized by the direct polycondensation reaction of 4,4'-azodibenzoic acid 2 with 4,4'-diamino diphenyl sulfone 3 in the presence of triphenyl phosphate (TPP), CaCl2, pyridine and N-methyl-2-pyrrolidone (NMP). Morphology and structure of the resulting PA-nanocomposite films 4a and 4b with 10 and 20% silicate particles were characterized by FTIR spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of clay dispersion and the interaction between clay and polymeric chains on the properties of nanocomposite films were investigated by using Uv-vis spectroscopy, thermogravimetric analysis (TGA) and water uptake measurements.

Genomic characterization of putative allergen genes in peach/almond and their synteny with apple

PubMed Central

Chen, Lin; Zhang, Shuiming; Illa, Eudald; Song, Lijuan; Wu, Shandong; Howad, Werner; Arús, Pere; Weg, Eric van de; Chen, Kunsong; Gao, Zhongshan

2008-01-01

Background Fruits from several species of the Rosaceae family are reported to cause allergic reactions in certain populations. The allergens identified belong to mainly four protein families: pathogenesis related 10 proteins, thaumatin-like proteins, lipid transfer proteins and profilins. These families of putative allergen genes in apple (Mal d 1 to 4) have been mapped on linkage maps and subsequent genetic study on allelic diversity and hypoallergenic traits has been carried out recently. In peach (Prunus persica), these allergen gene families are denoted as Pru p 1 to 4 and for almond (Prunus dulcis)Pru du 1 to 4. Genetic analysis using current molecular tools may be helpful to establish the cause of allergenicity differences observed among different peach cultivars. This study was to characterize putative peach allergen genes for their genomic sequences and linkage map positions, and to compare them with previously characterized homologous genes in apple (Malus domestica). Results Eight Pru p/du 1 genes were identified, four of which were new. All the Pru p/du 1 genes were mapped in a single bin on the top of linkage group 1 (G1). Five Pru p/du 2 genes were mapped on four different linkage groups, two very similar Pru p/du 2.01 genes (A and B) were on G3, Pru p/du 2.02 on G7,Pru p/du 2.03 on G8 and Pru p/du 2.04 on G1. There were differences in the intron and exon structure in these Pru p/du 2 genes and in their amino acid composition. Three Pru p/du 3 genes (3.01–3.03) containing an intron and a mini exon of 10 nt were mapped in a cluster on G6. Two Pru p/du 4 genes (Pru p/du 4.01 and 4.02) were located on G1 and G7, respectively. The Pru p/du 1 cluster on G1 aligned to the Mal d 1 clusters on LG16; Pru p/du 2.01A and B on G3 to Mal d 2.01A and B on LG9; the Pru p/du 3 cluster on G6 to Mal d 3.01 on LG12; Pru p/du 4.01 on G1 to Mal d 4.03 on LG2; and Pru p/du 4.02 on G7 to Mal d 4.02 on LG2. Conclusion A total of 18 putative peach/almond allergen genes have been mapped on five linkage groups. Their positions confirm the high macro-synteny between peach/almond and apple. The insight gained will help to identify key genes causing differences in allergenicity among different cultivars of peach and other Prunus species. PMID:19014629

Organo-Soluble Porphyrin Mixed Monolayer-Protected Gold Nanorods with Intercalated Fullerenes

DTIC Science & Technology

2012-03-16

Mixed Monolayer- Protected Gold Nanorods with Intercalated Fullerenes Chenming Xue, Yongqian Xu, Yi Pang, Dingshan Yu, Liming Dai, Min Gao, Augustine...Protected Gold Nanorods with Intercalated Fullerenes 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT... Fullerenes Chenming Xue, † Yongqian Xu, ‡ Yi Pang, ‡ Dingshan Yu, § Liming Dai, § Min Gao, † Augustine Urbas ± and Quan

Evaluation of Carbon Anodes for Rechargeable Lithium Cells

NASA Technical Reports Server (NTRS)

Huang, C-K.; Surampudi, S.; Attia, A.; Halpert, G.

1993-01-01

Both liquid phase intercalation technique and electrochemical intercalation technique were examined for the Li-carbon material preparation. The electrochemical techniques include a intermittent discharge method and a two step method. These two electrochemical techniques can ensure to achieve the maximum reversible Li capacity for common commercially available carbon materials. The carbon materials evaluated by the intercalacation method includes: pitch coke, petroleum cole, PAN fiber and graphite materials. Their reversible Li capacity were determined and compared. In this paper, we also demonstrate the importance of EPDM binder composition in the carbon electrode. Our results indicated that it can impact the Li intercalation and de-intercalation capacity in carbon materials. Finally, two possibilities that may help explain the capacity degradation during practical cell cycling were proposed.

Preparation of 5-benzotriazolyl-4-hydroxy-3- sec-butylbenzenesulfonate anion-intercalated layered double hydroxide and its photostabilizing effect on polypropylene

NASA Astrophysics Data System (ADS)

Li, Dianqing; Tuo, Zhenjun; Evans, David G.; Duan, Xue

2006-10-01

An organic UV absorber has been intercalated into a layered double hydroxide (LDH) host by ion-exchange method using ZnAl-NO 3-LDH as a precursor with an aqueous solution of the sodium salt of 5-benzotriazolyl-4-hydroxy-3- sec-butylbenzenesulfonic acid (BZO). After intercalation of the UV absorber, the interlayer distance in the LDHs increases from 0.89 to 2.32 nm. Infrared spectra and thermogravimetry and differential thermal analysis (TG-DTA) curves reveal the presence of a complex system of supramolecular host-guest interactions. The thermostability of BZO is markedly enhanced by intercalation in the LDH host. ZnAl-BZO-LDHs/polypropylene composite materials exhibit excellent UV photostability.

Powder, paper and foam of few-layer graphene prepared in high yield by electrochemical intercalation exfoliation of expanded graphite.

PubMed

Wu, Liqiong; Li, Weiwei; Li, Peng; Liao, Shutian; Qiu, Shengqiang; Chen, Mingliang; Guo, Yufen; Li, Qi; Zhu, Chao; Liu, Liwei

2014-04-09

A facile and high-yield approach to the preparation of few-layer graphene (FLG) by electrochemical intercalation exfoliation (EIE) of expanded graphite in sulfuric acid electrolyte is reported. Stage-1 H2SO4-graphite intercalation compound is used as a key intermediate in EIE to realize the efficient exfoliation. The yield of the FLG sheets (<7 layers) with large lateral sizes (tens of microns) is more than 75% relative to the total amount of starting expanded graphite. A low degree of oxygen functionalization existing in the prepared FLG flakes enables them to disperse effectively, which contributes to the film-forming characteristics of the FLG flakes. These electrochemically exfoliated FLG flakes are integrated into several kinds of macroscopic graphene structures. Flexible and freestanding graphene papers made of the FLG flakes retain excellent conductivity (≈24,500 S m(-1)). Three-dimensional (3D) graphene foams with light weight are fabricated from the FLG flakes by the use of Ni foams as self-sacrifice templates. Furthermore, 3D graphene/Ni foams without any binders, which are used as supercapacitor electrodes in aqueous electrolyte, provide the specific capacitance of 113.2 F g(-1) at a current density of 0.5 A g(-1), retaining 90% capacitance after 1000 cycles. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photocatalytic oxidation of aqueous ammonia over microwave-induced titanate nanotubes.

PubMed

Ou, Hsin-Hung; Liao, Ching-Hui; Liou, Ya-Hsuan; Hong, Jian-Hao; Lo, Shang-Lien

2008-06-15

Characterizations of microwave-induced titanate nanotubes (NaxH(2-x)Ti3O7, TNTs) were conducted by the determinations of specific surface area (S(BET)), X-ray diffraction (XRD), X-ray photoelectron spectroscopic (XPS), ionic coupled plasma-atomic emission spectrometry(ICP-AES), scanning electron microscopy/ energy dispersive X-ray (SEM/EDX), and high-resolution transmission electron microscopy (HR-TEM). The applied level of microwave irradiation during the fabrication process is responsible for both the intercalation intensity of Na atoms into TNTs and the type of crystallization phase within TNTs, which dominate the efficiency of photocatalytic NH3/NH4+. A pure TNT phase presents no powerful ability toward photocatalytic NH3/ NH4+, while the photocatalytic efficiency can be enhanced with the presence of a rutile phase within TNTs. In addition, the mixture of anatase and rutile phase within P25 TiO2 prefers forming NO3-, whereas TNTs yield higher NO2- amount Regarding the effect of acid-washing treatment on TNTs, the acid-treated TNTs with enhanced ion exchangeability considerably improve the NH3/NH4+ degradation and NO2-/NO3- yields. This result is likely ascribed to the easy intercalation of NH3/ NH4+ into the structure of acid-washing TNTs so that the photocatalytic oxidation of intercalated NH3/NH4+ is not limited to the shielding effect resulting from the overload of TNTs.

Physicochemical properties of nanocomposite: Hydroxyapatite in reduced graphene oxide.

PubMed

Rajesh, A; Mangamma, G; Sairam, T N; Subramanian, S; Kalavathi, S; Kamruddin, M; Dash, S

2017-07-01

Graphene oxide (GO) based nanocomposites have gained considerable attention in the field of material science due to their excellent physicochemical and biological properties. Incorporation of nanomaterials into GO sheets prevents the formation of π-π stacking bond thereby giving rise to composites that show the improved properties compared to their individual counterparts. In this work, reduced graphene oxide (rGO) - hydroxyapatite (HAP) nanocomposites were synthesized by ultrasonic method. Increasing the c/a ratio of HAP in the diffraction pattern of rGO/HAP nanocomposites indicates the c-axis oriented grown HAP nanorods interacting with rGO layers. Shift in wavenumber (15cm -1 ) and increase of full width at half maximum (45cm -1 ) of G band in Raman spectra of the rGO/HAP nanocomposites are observed and attributed to the tensile strain induced due to the intercalated HAP nanorods between the rGO layers. Atomic force microscopy (AFM) and phase imaging studies revealed the intercalation of HAP nanorod with diameter 30nm and length 110-120nm in rGO sheets was clearly perceived along with improved elasticity compared to pristine HAP. 13 C-NMR results proved the synergistic interaction between both components in rGO/HAP nanocomposite. The novel properties observed and the microscopic mechanism responsible for this are a result of the structural modification in rGO layers brought about by the intercalation of HAP nanorods. Copyright © 2017. Published by Elsevier B.V.

Proflavine binding to poly(rC-rA) inverts the CD spectrum but not the helix handedness.

PubMed

Westhof, E; Sundaralingam, M

1984-08-01

The interaction of proflavine hemisulfate with the sodium salt of poly(rC-rA) in solution (unbuffered) yields an inverted (mirror-like) circular dichroism (CD) spectrum to that of the free poly(rC-rA). Simultaneously, an induced negative Cotton effect appears in the proflavine band region with a maximum at 467 nm and a slight shoulder at 420 nm. This observation may be explained as resulting from the formation of a poly(rC-rA).proflavine complex with the polynucleotide existing as a right-handed parallel chain duplex with the proflavine intercalated between the CpA sequence and not the ApC sequence. The intercalation geometry here is expected to be analogous to that found in the crystal structure of the dinucleotide CpA.proflavine complex (Westhof et al. J. Mol. Biol., 1981) which forms a miniature right-handed helix. Although normally an inverted spectra could be attributed to a reversal in the helix handedness, the similarity in the 31P nuclear magnetic resonance spectra between the free and proflavine bound poly(rC-rA) indicates that their handedness is the same. The inverted CD spectrum may be a result of the different stacking orientation between the intercalated proflavine and the A-A base-pair on one hand and the triply hydrogen bonded protonated C-C base-pair on the other.

Toward efficient Zn(II)-based artificial nucleases.

PubMed

Boseggia, Elisa; Gatos, Maddalena; Lucatello, Lorena; Mancin, Fabrizio; Moro, Stefano; Palumbo, Manlio; Sissi, Claudia; Tecilla, Paolo; Tonellato, Umberto; Zagotto, Giuseppe

2004-04-14

A series of cis-cis-triaminocyclohexane Zn(II) complex-anthraquinone intercalator conjugates, designed in such a way to allow their easy synthesis and modification, have been investigated as hydrolytic cleaving agents for plasmid DNA. The ligand structure comprises a triaminocyclohexane platform linked by means of alkyl spacers of different length (from C(4) to C(8)) to the anthraquinone group which may intercalate the DNA. At a concentration of 5 microM, the complex of the derivative with a C(8) alkyl spacer induces the hydrolytic stand scission of supercoiled DNA with a rate of 4.6 x 10(-6) s(-1) at pH 7 and 37 degrees C. The conjugation of the metal complex with the anthraquinone group leads to a 15-fold increase of the cleavage efficiency when compared with the anthraquinone lacking Zn-triaminocyclohexane complex. The straightforward synthetic procedure employed, allowing a systematic change of the spacer length, made possible to gain more insight on the role of the intercalating group in determining the reactivity of the systems. Comparison of the reactivity of the different complexes shows a remarkable increase of the DNA cleaving efficiency with the length of the spacer. In the case of too-short spacers, the advantages due to the increased DNA affinity are canceled due to the incorrect positioning of the reactive group, thus leading to cleavage inhibition.

Cohesive Energies of Some Transition Metal Compounds Using Embedded Clusters

NASA Astrophysics Data System (ADS)

Press, Mehernosh Rustom

The molecular-clusters approach to electronic structure calculation is especially well-suited to the study of properties that depend primarily on the local environment of a system, especially those with no translational symmetry, e.g. systems with defects and structural deformations. The presence of the rest of the crystal environment can be accounted for approximately by embedding the cluster in a self-consistent crystal potential. This thesis makes a contribution in the area of investigating the capability of embedded molecular-clusters to yield reliable bulk structural properties. To this end, an algorithm for calculating the cohesive energies of clusters within the discrete-variational X(,(alpha)) LCAO-MO formulation is set up and verified on simple solids: Li, Na, Cu and LiF. We then use this formulation to study transition metal compounds, for which the interesting physics lies in local lattice defects, foreign impurities and structural deformations. In a self -consistent calculation of the lattice energies and stability of defect clusters in wustite, Fe(,1-x)O, corner-sharing aggregates of the 4:1 defect are identified as the most stable defect configurations due to efficient compensation of the cluster charge. The intercalation properties of layered-transition-metal-dichalcogenides continues to be a fertile experimental working area, backed by comparatively little theoretical study. We find that intercalation of ZrS(,2) with Na perturbs the valence energy level structure sufficiently to induce a more ionic Zr-S bond, a narrowing of the optical gap and filling of the lowest unoccupied host lattice orbitals with the electron donated by Na. Fe - intercalation in ZrS(,2) is accommodated via a strong Fe-S bond, impurity-like band levels in the optical gap of the host and hybridization-driven compression and lowering of the conduction band energy levels. The piezoelectric cuprous halides, CuCl and CuBr, exhibit a host of intriguing properties due to a filled and very active d('10) shell at the Fermi energy. A self-consistent calculation via energy minimization of the internal strain in these compounds shows both Cu-halide bonds to be very rigid with little charge delocalization under strain. Piezoelectric response is calculated in terms of effective charges and quadrupolar moments, e(,T) and (DELTA)Q.

Drug delivery system for an anticancer agent, chlorogenate-Zn/Al-layered double hydroxide nanohybrid synthesised using direct co-precipitation and ion exchange methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barahuie, Farahnaz; Hussein, Mohd Zobir, E-mail: mzobir@putra.upm.edu.my; Arulselvan, Palanisamy

A nano-structured drug-inorganic clay hybrid involving an active anticancer compound, which is chlorogenic acid (CA) intercalated into Zn/Al-layered double hydroxide, has been assembled via ion-exchange and co-precipitation methods to form a nanohybrid CZAE (a chlorogenic acid-Zn/Al nanohybrid synthesised using an ion-exchange method) and CZAC (a chlorogenic acid-Zn/Al nanohybrid synthesised using a direct method), respectively. The X-ray diffraction (XRD) results confirmed that the CA-LDH had a hybrid structure in which the anionic chlorogenate is arranged between the interlayers as a horizontal monolayer at 90 and 20° angles from the x axis for CZAE and CZAC, respectively. Both nanohybrids have the propertiesmore » of mesoporous materials. The high loading percentage of chlorogenic acid (approximately 43.2% for CZAE and 45.3% for CZAC) with basal spacings of 11.7 and 12.6 Å for CZAE and CZAC, respectively, corroborates the successful intercalation of chlorogenic acid into the interlayer gallery of layered double hydroxides. Free chlorogenic acid and the synthesised nanocomposites (CZAE, CZAC) were assessed for their cytotoxicity against various cancer cells. The Fourier transform infrared data supported the formation of both nanohybrids, and a thermal analysis showed that the nanohybrids are more thermally stable than their counterparts. The chlorogenate shows a sustained release, and the release rate of chlorogenate from CZAE and CZAC nanohybrids at pH 7.4 is remarkably lower than that at pH 4.8 due to their different release mechanisms. The release rate of chlorogenate from both nanohybrids can be described as pseudo-second order. The present investigation revealed the potential of the nanohybrids to enhance the in vitro anti-tumour effect of chlorogenic acid in liver and lung cancer cells in vitro. - Highlights: • We intercalated chlorogenic into Zn/Al-layered double hydroxide by ion-exchange and coprecipitation methods. • The two methods gave nanocomposites with slightly different physico-chemical properties. • Chlorogenate-zinc aluminium layered double hydroxide nanohybrids have the potential to be used as a controlled release formulation. • The thermal stability of chlorogenic acid is markedly enhanced upon the intercalation process. • The inhibition of cancer cell growth is higher for nanohybrids than for free chlorogenic acid.« less

Adsorption mechanism of ester phosphate on baryum titanate in organic medium. Preliminary results on the structure of the adsorbed layer

NASA Astrophysics Data System (ADS)

Le Bars, N.; Tinet, D.; Faugère, A. M.; van Damme, H.; Levitz, P.

1991-05-01

The purpose of this work is to evidence the adsorption mechanism and the structure of commercial phosphate ester surfactant stabilized BaTiO3 in organic suspension, and to relate these characteristics to rheological behaviour. Binders and plasticizers are omitted to reduce the number of system components. Firstly adsorption isotherm were determined by inductively coupled argon plasma technique and interpretated based on transmission electron microscopy and ^{31}P nuclear magnetic resonance studies. Preliminary rheological measurements were then performed and related to suspension structure. Structure of the adsorption layer is critically discussed. L'objectif de cette étude est la compréhension du mécanisme d'adsorption d'agents dispersants phosphatés dans des suspensions organiques de BaTiO3, ainsi que la caractérisation de la structure, et du comportement rhéologique de ces suspensions. Liants et plastifiants ne sont pas utilisés, afin de réduire le nombre de composants dans le système. Dans un premier temps, l'isotherme d'adsorption est établie par dosage en émission plasma, puis interprétée sur la base de résultats de Microscopie Eloctronique à Transmission, et de spectroscopie par Résonance Magnétique Nucléaire du ^{31}P. Des mesures rhéologiques préliminaires sont effectuées pour caractériser la structure des suspensions.

Intercalated graphitic carbon nitride: a fascinating two-dimensional nanomaterial for an ultra-sensitive humidity nanosensor

NASA Astrophysics Data System (ADS)

Zhang, Zhenyi; Huang, Jindou; Yuan, Qing; Dong, Bin

2014-07-01

We develop a novel humidity nanosensor based on intercalated graphitic carbon nitride (g-C3N4) nanosheets fabricated by a facile thermal polymerization of common urea in the presence of LiCl as the intercalated guest under air and ambient pressure. The response and recovery times of an optimal nanosensor can reach ~0.9 s and ~1.4 s, respectively, which are superior to most of the traditional oxide ceramic-based humidity nanosensors tested under similar conditions. By combining with the theoretical calculations, it is proposed that the ultrafast response-recovery time for this nanosensor is attributed to their unique 2D intercalated nanostructure by which Li species linked with the ``nitrogen pots'' of g-C3N4 can make the protons conduct in the first adsorbed water layer. Meanwhile, the physically adsorbed water on the surface of LiCl-intercalated g-C3N4 nanosheets can be desorbed rapidly at a relative lower RH environment due to their high adsorption energy and the strong diffusion effect of water molecules.We develop a novel humidity nanosensor based on intercalated graphitic carbon nitride (g-C3N4) nanosheets fabricated by a facile thermal polymerization of common urea in the presence of LiCl as the intercalated guest under air and ambient pressure. The response and recovery times of an optimal nanosensor can reach ~0.9 s and ~1.4 s, respectively, which are superior to most of the traditional oxide ceramic-based humidity nanosensors tested under similar conditions. By combining with the theoretical calculations, it is proposed that the ultrafast response-recovery time for this nanosensor is attributed to their unique 2D intercalated nanostructure by which Li species linked with the ``nitrogen pots'' of g-C3N4 can make the protons conduct in the first adsorbed water layer. Meanwhile, the physically adsorbed water on the surface of LiCl-intercalated g-C3N4 nanosheets can be desorbed rapidly at a relative lower RH environment due to their high adsorption energy and the strong diffusion effect of water molecules. Electronic supplementary information (ESI) available: Fig. S1-S8 and Table S1 including SEM, TEM and theoretical calculations. See DOI: 10.1039/c4nr01570c

Solution structure and base pair opening kinetics of the i-motif dimer of d(5mCCTTTACC): a noncanonical structure with possible roles in chromosome stability.

PubMed

Nonin, S; Phan, A T; Leroy, J L

1997-09-15

Repetitive cytosine-rich DNA sequences have been identified in telomeres and centromeres of eukaryotic chromosomes. These sequences play a role in maintaining chromosome stability during replication and may be involved in chromosome pairing during meiosis. The C-rich repeats can fold into an 'i-motif' structure, in which two parallel-stranded duplexes with hemiprotonated C.C+ pairs are intercalated. Previous NMR studies of naturally occurring repeats have produced poor NMR spectra. This led us to investigate oligonucleotides, based on natural sequences, to produce higher quality spectra and thus provide further information as to the structure and possible biological function of the i-motif. NMR spectroscopy has shown that d(5mCCTTTACC) forms an i-motif dimer of symmetry-related and intercalated folded strands. The high-definition structure is computed on the basis of the build-up rates of 29 intraresidue and 35 interresidue nuclear Overhauser effect (NOE) connectivities. The i-motif core includes intercalated interstrand C.C+ pairs stacked in the order 2*.8/1.7*/1*.7/2.8* (where one strand is distinguished by an asterisk and the numbers relate to the base positions within the repeat). The TTTA sequences form two loops which span the two wide grooves on opposite sides of the i-motif core; the i-motif core is extended at both ends by the stacking of A6 onto C2.C8+. The lifetimes of pairs C2.C8+ and 5mC1.C7+ are 1 ms and 1 s, respectively, at 15 degrees C. Anomalous exchange properties of the T3 imino proton indicate hydrogen bonding to A6 N7 via a water bridge. The d(5mCCTTTTCC) deoxyoligonucleotide, in which position 6 is occupied by a thymidine instead of an adenine, also forms a symmetric i-motif dimer. However, in this structure the two TTTT loops are located on the same side of the i-motif core and the C.C+ pairs are formed by equivalent cytidines stacked in the order 8*.8/1.1*/7*.7/2.2*. Oligodeoxynucleotides containing two C-rich repeats can fold and dimerize into an i-motif. The change of folding topology resulting from the substitution of a single nucleoside emphasizes the influence of the loop residues on the i-motif structure formed by two folded strands.

Zerovalent Copper Intercalated Birnessite as a Cathode for Lithium Ion Batteries: Extending Cycle Life

DOE PAGES

Li, Yue Ru; Poyraz, Altug S.; Hu, Xiaobing; ...

2017-01-01

Birnessite type layered manganese dioxides (δ-MnO 2) have attracted considerable attention in recent years as 2D intercalation cathodes for rechargeable Li +, Na +, and Mg 2+ batteries due to fast ion diffusion through their negatively charged δ-MnO 2 sheets separated by interlayer cations and a stable Mn 3+/4+ redox couple. Here we report the preparation and electrochemistry of zero and divalent copper co-intercalated birnessite type manganese dioxide (Cu 0 0.03Cu 2+ 0.21Na 0.12MnO 2·0.9H 2O). The copper intercalated birnessite materials were fully characterized utilizing powder X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), transmission electron microscopy (TEM).more » The mixed valent nature of intercalated Cu 0 and Cu 2+ was confirmed by X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS). Electrochemical evaluation results show that zero valent copper intercalated birnessite exhibits higher discharge capability, improved cyclability, and lower impedance compared to the Cu 2+ only intercalated (Cu 0.26MnO 2·1.0H 2O) and Cu free Na birnessite (Na 0.40MnO 2·1.0H 2O) materials. Remarkably, zero valent copper birnessite shows almost no fade after 10 cycles at 0.1 mV/s. Electrochemical impedance spectroscopy results suggest that charge transfer resistivity of Cu 0 modified samples was much lower than that of Cu 2+ and Cu free birnessite, indicating that the presence of a small amount of Cu 0 improves the conductivity of birnessite and results in better electrochemical cyclability, rate capability, and lower impedance.« less

Enhancing the efficiency of lithium intercalation in carbon nanotube bundles using surface functional groups.

PubMed

Xiao, Shiyan; Zhu, Hong; Wang, Lei; Chen, Liping; Liang, Haojun

2014-08-14

The effect of surface functionalization on the ability and kinetics of lithium intercalation in carbon nanotube (CNT) bundles has been studied by comparing the dynamical behaviors of lithium (Li) ions in pristine and -NH2 functionalized CNTs via ab initio molecular dynamics simulations. It was observed that lithium intercalation has been achieved quickly for both the pristine and surface functionalized CNT bundle. Our calculations demonstrated for the first time that CNT functionalization improved the efficiency of lithium intercalation significantly at both low and high Li ion density. Moreover, we found that keeping the nanotubes apart with an appropriate distance and charging the battery at a rational rate were beneficial to achieve a high rate of lithium intercalation. Besides, the calculated adsorption energy curves indicated that the potential wells in the system of -NH2 functionalized CNT were deeper than that of the pristine CNT bundle by 0.74 eV, and a third energy minimum with a value of 2.64 eV existed at the midpoint of the central axis of the nanotube. Thus, it would be more difficult to remove Li ions from the nanotube interior after surface functionalization. The barrier for lithium diffusion in the interior of the nanotube is greatly decreased because of the surface functional groups. Based on these results, we would suggest to "damage" the nanotube by introducing defects at its sidewall in order to improve not only the capacity of surface functionalized CNTs but also the efficiency of lithium intercalation and deintercalation processes. Our results presented here are helpful in understanding the mechanism of lithium intercalation into nanotube bundles, which may potentially be applied in the development of CNT based electrodes.

Physicochemical characterization of Capstone depleted uranium aerosols III: morphologic and chemical oxide analyses.

PubMed

Krupka, Kenneth M; Parkhurst, Mary Ann; Gold, Kenneth; Arey, Bruce W; Jenson, Evan D; Guilmette, Raymond A

2009-03-01

The impact of depleted uranium (DU) penetrators against an armored target causes erosion and fragmentation of the penetrators, the extent of which is dependent on the thickness and material composition of the target. Vigorous oxidation of the DU particles and fragments creates an aerosol of DU oxide particles and DU particle agglomerations combined with target materials. Aerosols from the Capstone DU aerosol study, in which vehicles were perforated by DU penetrators, were evaluated for their oxidation states using x-ray diffraction (XRD), and particle morphologies were examined using scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS). The oxidation state of a DU aerosol is important as it offers a clue to its solubility in lung fluids. The XRD analysis showed that the aerosols evaluated were a combination primarily of U3O8 (insoluble) and UO3 (relatively more soluble) phases, though intermediate phases resembling U4O9 and other oxides were prominent in some samples. Analysis of particle residues in the micrometer-size range by SEM/EDS provided microstructural information such as phase composition and distribution, fracture morphology, size distribution, and material homogeneity. Observations from SEM analysis show a wide variability in the shapes of the DU particles. Some of the larger particles were spherical, occasionally with dendritic or lobed surface structures. Others appear to have fractures that perhaps resulted from abrasion and comminution, or shear bands that developed from plastic deformation of the DU material. Amorphous conglomerates containing metals other than uranium were also common, especially with the smallest particle sizes. A few samples seemed to contain small bits of nearly pure uranium metal, which were verified by EDS to have a higher uranium content exceeding that expected for uranium oxides. Results of the XRD and SEM/EDS analyses were used in other studies described in this issue of Health Physics to interpret the results of lung solubility studies and in selecting input parameters for dose assessments.

Electrochemical potassium-ion intercalation in NaxCoO2: a novel cathode material for potassium-ion batteries.

PubMed

Sada, Krishnakanth; Senthilkumar, Baskar; Barpanda, Prabeer

2017-07-27

Reversible electrochemical potassium-ion intercalation in P2-type Na x CoO 2 was examined for the first time. Hexagonal Na 0.84 CoO 2 platelets prepared by a solution combustion synthesis technique were found to work as an efficient host for K + intercalation. They deliver a high reversible capacity of 82 mA h g -1 , good rate capability and excellent cycling performance up to 50 cycles.

Lithium ion intercalation in thin crystals of hexagonal TaSe2 gated by a polymer electrolyte

NASA Astrophysics Data System (ADS)

Wu, Yueshen; Lian, Hailong; He, Jiaming; Liu, Jinyu; Wang, Shun; Xing, Hui; Mao, Zhiqiang; Liu, Ying

2018-01-01

Ionic liquid gating has been used to modify the properties of layered transition metal dichalcogenides (TMDCs), including two-dimensional (2D) crystals of TMDCs used extensively recently in the device work, which has led to observations of properties not seen in the bulk. The main effect comes from the electrostatic gating due to the strong electric field at the interface. In addition, ionic liquid gating also leads to ion intercalation when the ion size of the gate electrolyte is small compared to the interlayer spacing of TMDCs. However, the microscopic processes of ion intercalation have rarely been explored in layered TMDCs. Here, we employed a technique combining photolithography device fabrication and electrical transport measurements on the thin crystals of hexagonal TaSe2 using multiple channel devices gated by a polymer electrolyte LiClO4/Polyethylene oxide (PEO). The gate voltage and time dependent source-drain resistances of these thin crystals were used to obtain information on the intercalation process, the effect of ion intercalation, and the correlation between the ion occupation of allowed interstitial sites and the device characteristics. We found a gate voltage controlled modulation of the charge density waves and a scattering rate of charge carriers. Our work suggests that ion intercalation can be a useful tool for layered materials engineering and 2D crystal device design.

Influence of metal ions intercalation on the vibrational dynamics of water confined between MXene layers

DOE PAGES

Osti, Naresh C.; Naguib, Michael; Ganeshan, Karthik; ...

2017-11-21

Two-dimensional carbides and nitrides of early transition metals (MXenes) combine high conductivity with hydrophilic surfaces, which make them promising for energy storage, electrocatalysis, and water desalination. Effects of intercalated metal ions on the vibrational states of water confined in Ti 3C 2T x MXenes have been explored using inelastic neutron scattering (INS) and molecular dynamics simulations to better understand the mechanisms that control MXenes’ behavior in aqueous electrolytes, water purification and other important applications. Here, we observe INS signal from water in all samples, pristine and with lithium, sodium or potassium ions intercalated between the 2D Ti 3C 2T xmore » layers. However, only a small amount of water is found to reside in Ti 3C 2T x intercalated with metal ions. Water in pristine Ti 3C 2T x is more disordered, with bulk-like characteristics, in contrast to intercalated Ti 3C 2T x, where water is more ordered, irrespective of the metal ions used for intercalation. The ordering of the confined water increases with the ion size. Lastly, this finding is further confirmed from molecular dynamics simulation which showed an increase in interference of water molecules with increasing ion size resulting in a concomitant decrease in water mobility, therefore, providing a guidance to tailor MXene properties for energy and environmental applications.« less

Influence of metal ions intercalation on the vibrational dynamics of water confined between MXene layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osti, Naresh C.; Naguib, Michael; Ganeshan, Karthik

Two-dimensional carbides and nitrides of early transition metals (MXenes) combine high conductivity with hydrophilic surfaces, which make them promising for energy storage, electrocatalysis, and water desalination. Effects of intercalated metal ions on the vibrational states of water confined in Ti 3C 2T x MXenes have been explored using inelastic neutron scattering (INS) and molecular dynamics simulations to better understand the mechanisms that control MXenes’ behavior in aqueous electrolytes, water purification and other important applications. Here, we observe INS signal from water in all samples, pristine and with lithium, sodium or potassium ions intercalated between the 2D Ti 3C 2T xmore » layers. However, only a small amount of water is found to reside in Ti 3C 2T x intercalated with metal ions. Water in pristine Ti 3C 2T x is more disordered, with bulk-like characteristics, in contrast to intercalated Ti 3C 2T x, where water is more ordered, irrespective of the metal ions used for intercalation. The ordering of the confined water increases with the ion size. Lastly, this finding is further confirmed from molecular dynamics simulation which showed an increase in interference of water molecules with increasing ion size resulting in a concomitant decrease in water mobility, therefore, providing a guidance to tailor MXene properties for energy and environmental applications.« less

Stability of bromine, iodine monochloride, copper (II) chloride, and nickel (II) chloride intercalated pitch-based graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, James R.; Slabe, Melissa E.; Shaffer, Nanette

1987-01-01

Four different grades of pitch-based graphite fibers (Amoco P-55, P-75, P-100. and P-120) were intercalated with each of four different intercalates: bromine (Br2), iodine monochloride (ICl), copper (II) chloride (CuCl2), and nickel (II) chloride (NiCl2). The P-55 fibers did not react with Br2 or NiCl2, and the P-75 did not react with NiCl2. The stability of the electrical resistance of the intercalated fibers was monitored over long periods of time in ambient, high humidity (100 percent at 60 C), vacuum (10 to the -6 torr), and high temperature (up to 400 C) conditions. Fibers with lower graphitization form graphite intercalation compounds (GIC's) which are more stable than those with higher graphitization (i.e., P-55 (most stable) greater than P-75 greater than P-100 greater than P-120 (least stable). Br2 formed the most stable GIC's followed in order of decreasing stability by ICl, CuCl2, and NiCl2. While Br2 GIC's had the most stability, ICl had the advantages of forming GIC's with slightly greater reduction in resistance (by about 10%) than Br2, and the ability to intercalate P-55 fiber. Transition metal chlorides are susceptible to water vapor and high temperature. The stability of fibers in composites differs.

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

PubMed Central

2013-01-01

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

The Black Leader's Rhetorical Dilemma: An Analysis of the Debate Between W.E.B. DuBois and Booker T. Washington.

ERIC Educational Resources Information Center

Harris, Thomas E.

Improving the economic condition of the Negro was a fundamental concern of both W. E. B. DuBois and Booker T. Washington. It was Washington's view that the Negro should be willing to perform menial tasks as a means for gaining a foothold in the economic structure. He counseled the Negro to start at the bottom. Washington's philosophy centered on…

Polyethylene organo-clay nanocomposites: the role of the interface chemistry on the extent of clay intercalation/exfoliation.

PubMed

Mainil, Michaël; Alexandre, Michaël; Monteverde, Fabien; Dubois, Philippe

2006-02-01

High density polyethylene (HDPE)/clay nanocomposites have been prepared using three different functionalized polyethylene compatibilizers: an ethylene/vinyl acetate copolymer, a polyethylene grafted with maleic anhydride functions and a (styrene-b-ethylene/butylene-b-styrene) block copolymer. The nanocomposites were prepared via two different routes: (1) the dispersion in HDPE of a masterbatch prepared from the compatibilizer and the clay or (2) the direct melt blending of the three components. For each compatibilizer, essentially intercalated nanocomposites were formed as determined by X-ray diffraction and transmission electron microscopy. With the ethylene/vinyl acetate copolymer, a significant delamination of the intercalated clay in thin stacks was observed. This dispersion of thin intercalated stacks within the polymer matrix allowed increasing significantly the stiffness and the flame resistance of the nanocomposite. A positive effect of shear rate and blending time has also been put into evidence, especially for the process based on the masterbatch preparation, improving both the formation of thin stacks of intercalated clay and the mechanical properties and the flame resistance of the formed nanocomposites.

Dispersions of TiS2 nanosheets in organic medium

NASA Astrophysics Data System (ADS)

Manjunatha, S.; Kumar, A. Sunil; Machappa, T.

2018-05-01

Here in this article, we report Li-intercalated titanium disulfide (TiS2) two-dimensional (2D) nanosheets, exfoliated in 1-methyl-2-pyrrolidinone (NMP) forming a quite stable dispersions of pale brownish color. As synthesized TiS2 nanosheets were characterized by transmission electron microscopy (TEM). Selected area electron diffraction (SAED) pattern confirmed the hexagonal lattice structure of the exfoliated nanosheets.

Inorganic nanolayers: structure, preparation, and biomedical applications.

PubMed

Saifullah, Bullo; Hussein, Mohd Zobir B

2015-01-01

Hydrotalcite-like compounds are two-dimensional inorganic nanolayers also known as clay minerals or anionic clays or layered double hydroxides/layered hydroxy salts, and have emerged as a single type of material with numerous biomedical applications, such as drug delivery, gene delivery, cosmetics, and biosensing. Inorganic nanolayers are promising materials due to their fascinating properties, such as ease of preparation, ability to intercalate different type of anions (inorganic, organic, biomolecules, and even genes), high thermal stability, delivery of intercalated anions in a sustained manner, high biocompatibility, and easy biodegradation. Inorganic nanolayers have been the focus for researchers over the last decade, resulting in widening application horizons, especially in the field of biomedical science. These nanolayers have been widely applied in drug and gene delivery. They have also been applied in biosensing technology, and most recently in bioimaging science. The suitability of inorganic nanolayers for application in drug delivery, gene delivery, biosensing technology, and bioimaging science makes them ideal materials to be applied for theranostic purposes. In this paper, we review the structure, methods of preparation, and latest advances made by inorganic nanolayers in such biomedical applications as drug delivery, gene delivery, biosensing, and bioimaging.

Inorganic nanolayers: structure, preparation, and biomedical applications

PubMed Central

Saifullah, Bullo; Hussein, Mohd Zobir B

2015-01-01

Hydrotalcite-like compounds are two-dimensional inorganic nanolayers also known as clay minerals or anionic clays or layered double hydroxides/layered hydroxy salts, and have emerged as a single type of material with numerous biomedical applications, such as drug delivery, gene delivery, cosmetics, and biosensing. Inorganic nanolayers are promising materials due to their fascinating properties, such as ease of preparation, ability to intercalate different type of anions (inorganic, organic, biomolecules, and even genes), high thermal stability, delivery of intercalated anions in a sustained manner, high biocompatibility, and easy biodegradation. Inorganic nanolayers have been the focus for researchers over the last decade, resulting in widening application horizons, especially in the field of biomedical science. These nanolayers have been widely applied in drug and gene delivery. They have also been applied in biosensing technology, and most recently in bioimaging science. The suitability of inorganic nanolayers for application in drug delivery, gene delivery, biosensing technology, and bioimaging science makes them ideal materials to be applied for theranostic purposes. In this paper, we review the structure, methods of preparation, and latest advances made by inorganic nanolayers in such biomedical applications as drug delivery, gene delivery, biosensing, and bioimaging. PMID:26366081

Superstructure ZrV2O7 nanofibres: thermal expansion, electronic and lithium storage properties.

PubMed

Li, Qidong; Zhao, Yanming; Kuang, Quan; Fan, Qinghua; Dong, Youzhong; Liu, Xudong

2016-11-30

ZrV 2 O 7 has attracted much attention as a negative thermal expansion (NTE) material due to its isotropic negative structure. However, rarely has investigation of the lithium storage behaviors been carried out except our first report on it. Meanwhile, the electrochemical behaviors and energy storage characteristics have not been studied in depth and will be explored in this article. Herein, we report on the synthesis, characterization and lithium intercalation mechanism of superstructure ZrV 2 O 7 nanofibres that were prepared through a facile solution-based method with a subsequent annealing process. The thermal in situ XRD technique combined with the Rietveld refinement method is adopted to analyze the change in the temperature-dependent crystal structure. Benefiting from the nanostructured morphology and relatively high electronic conductivity, it presents acceptable cyclic stability and rate capability. According to the operando evolution of the XRD patterns obtained from electrochemical in situ measurements, the Li intercalation mechanism of the solid solution process with a subsequent conversion reaction can be concluded. Finally, the amorphous state of the electrodes after the initial fully discharged state can effectively enhance the electrochemical performances.