Sample records for cationic intermediate stabilization

  1. Controlling the thermodynamic stability of intermediate phases in a cationic-amphiphile-water system with strongly binding counterions. (United States)

    Gupta, Santosh Prasad; Raghunathan, V A


    We have studied the influence of two structurally isomeric organic salts, namely, 2-sodium-3-hydroxy naphthoate (SHN) and 1-sodium-2-hydroxy naphthoate (SHN1), on the phase behavior of concentrated aqueous solutions of the cationic surfactant cetylpyridinium chloride (CPC). Partial phase diagrams of the two systems have been constructed using polarizing optical microscopy and x-ray diffraction techniques. A variety of intermediate phases is seen in both systems for a range of salt concentrations. The CPC-SHN-water system exhibits the rhombohedral and tetragonal mesh phases in addition to the random mesh phase, whereas the CPC-SHN1-water system shows only the tetragonal and random mesh phases. The CPC-SHN-water system also exhibits two nematic phases consisting of cylindrical and disk-like micelles at relatively low and high salt concentrations, respectively. These results show that the concentration of the strongly bound counterion provided by the organic salt can be used as a control parameter to tune the stability of different intermediate phases in amphiphile-water systems.

  2. Metal Cations in G-Quadruplex Folding and Stability (United States)

    Bhattacharyya, Debmalya; Mirihana Arachchilage, Gayan; Basu, Soumitra


    This review is focused on the structural and physico-chemical aspects of metal cation coordination to G-Quadruplexes (GQ) and their effects on GQ stability and conformation. G-Quadruplex structures are non-canonical secondary structures formed by both DNA and RNA. G-quadruplexes regulate a wide range of important biochemical processes. Besides the sequence requirements, the coordination of monovalent cations in the GQ is essential for its formation and determines the stability and polymorphism of GQ structures. The nature, location and dynamics of the cation coordination and their impact on the overall GQ stability are dependent on several factors such as the ionic radii, hydration energy and the bonding strength to the O6 of guanines. The intracellular monovalent cation concentration and the localized ion concentrations determine the formation of GQs and can potentially dictate their regulatory roles. A wide range of biochemical and biophysical studies on an array of GQ enabling sequences have generated at a minimum the knowledge base that allows us to often predict the stability of GQs in presence of the physiologically relevant metal ions, however, prediction of conformation of such GQs is still out of the realm.

  3. Metal Cations in G-Quadruplex Folding and Stability (United States)

    Bhattacharyya, Debmalya; Mirihana Arachchilage, Gayan; Basu, Soumitra


    This review is focused on the structural and physicochemical aspects of metal cation coordination to G-Quadruplexes (GQ) and their effects on GQ stability and conformation. G-quadruplex structures are non-canonical secondary structures formed by both DNA and RNA. G-quadruplexes regulate a wide range of important biochemical processes. Besides the sequence requirements, the coordination of monovalent cations in the GQ is essential for its formation and determines the stability and polymorphism of GQ structures. The nature, location, and dynamics of the cation coordination and their impact on the overall GQ stability are dependent on several factors such as the ionic radii, hydration energy, and the bonding strength to the O6 of guanines. The intracellular monovalent cation concentration and the localized ion concentrations determine the formation of GQs and can potentially dictate their regulatory roles. A wide range of biochemical and biophysical studies on an array of GQ enabling sequences have generated at a minimum the knowledge base that allows us to often predict the stability of GQs in the presence of the physiologically relevant metal ions, however, prediction of conformation of such GQs is still out of the realm. PMID:27668212

  4. Influence of various functional groups on the relative stability of alkylperoxy triplet cations: A theoretical study (United States)

    Smith, Kenneth J.; Meloni, Giovanni


    CBS-QB3 energy calculations show that the formation of a stable triplet cation for alkylperoxy radicals is dependent on factors other than the stability of the daughter cations exclusively. We have found that in cases where the daughter ions are not capable of stabilizing the cation through hyperconjugation, it is possible for the triplet cation to be bound. In many circumstances, CBS-QB3 calculations have found bound triplet cation states with 'negative dissociation energies.' These results are attributed to the effects that electron donating/withdrawing substituents have on the spin and charge densities of the resulting cations.

  5. Intermediate-range chemical ordering of cations in molten RbCl-AgCl

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    Tahara, S. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Kawakita, Y. [J-PARC Center, Japan Atomic Energy Agency (JAEA), Ibaraki 319-1195 (Japan); Shimakura, H. [Faculty of Pharmacy, Niigata University of Pharmacy and Applied Life Sciences, Niigata 956-8603 (Japan); Ohara, K. [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Fukami, T. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Takeda, S. [Department of Physics, Faculty of Sciences, Kyushu University, Fukuoka 812-8581 (Japan)


    A first sharp diffraction peak (FSDP) is observed in the X-ray total structure factor of a molten mixture of RbCl-AgCl, while both pure melts of RbCl and AgCl do not exhibit FSDP individually. Molecular dynamics simulations were performed to investigate the origin of the FSDP with the polarizable ion model (PIM). Coexistence of covalent Ag–Cl and ionic Rb–Cl bonds leads the system to evolve intermediate range ordering, which is simulated by introducing the induced polarization in different ways between Ag–Cl with fully polarizable treatment based on Vashishta-Raman potential and Rb–Cl with suppression over-polarization in the nearest neighbor contribution based on Born-Meyer potential. The partial structure factors for both the Ag–Ag and Rb–Rb correlations, S{sub AgAg}(Q) and S{sub RbRb}(Q), show a positive contribution to the FSDP, while S{sub AgRb}(Q) for the Ag–Rb correlation exhibits a negative contribution, indicating that Ag and Rb ions are distributed in an alternating manner within the intermediate-range length scale. The origin of the intermediate-range chemical ordering of cations can be ascribed to the preferred direction of the dipole moments of anions in the PIM.

  6. Effect of cation trapping on thermal stability of magnetite nanoparticles. (United States)

    Pati, S S; Philip, John


    We investigate the effect of sodium trapping on thermal stability of magnetite (Fe3O4) nanoparticles. The pure magnetite nanoparticles incubated in sodium hydroxide solutions and subsequently washed with water to remove the excess sodium. The amount of sodium in magnetite is measured using atomic absorption spectroscopy. The size distribution obtained from Small angle X-ray scattering measurements show that particles are fairly monodisperse. The FTIR spectra of nanoparticles show transmission bands at 441 and 611 cm(-1) are due to the symmetric stretching vibrations (v) of Fe-O in octahedral and tetrahedral sites respectively. With 500 ppm of sodium ions (Na+) in magnetite, the cubic ferrite structure of maghemite (gamma-Fe2O3) to hexagonal hematite (alpha-Fe2O3) phase transition is enhanced by -150 degrees C in air. The Rietveld analysis of sodium doped magnetite nanoparticles show that above 99% of metastable gamma-Fe2O3 is converted to a thermodynamically stable alpha-Fe2O3 after air annealing at 700 degrees C. A decrease in enthalpy observed in doped magnetite unambiguously confirms that the activation energy for maghemite to hematite transition is increased due to the presence of trapped sodium ions. These results suggest that the trapped cations in ferrite nanoparticles can stabilize them by increasing the activation energy.

  7. Contributions of cation-π interactions to the collagen triple helix stability. (United States)

    Chen, Chia-Ching; Hsu, Wei; Hwang, Kuo-Chu; Hwu, Jih Ru; Lin, Chun-Cheng; Horng, Jia-Cherng


    Cation-π interactions are found to be an important noncovalent force in proteins. Collagen is a right-handed triple helix composed of three left-handed PPII helices, in which (X-Y-Gly) repeats dominate in the sequence. Molecular modeling indicates that cation-π interactions could be formed between the X and Y positions in adjacent collagen strands. Here, we used a host-guest peptide system: (Pro-Hyp-Gly)(3)-(Pro-Y-Gly-X-Hyp-Gly)-(Pro-Hyp-Gly)(3), where X is an aromatic residue and Y is a cationic residue, to study the cation-π interaction in the collagen triple helix. Circular dichroism (CD) measurements and Tm data analysis show that the cation-π interactions involving Arg have a larger contribution to the conformational stability than do those involving Lys, and Trp forms a weaker cation-π interaction with cationic residues than expected as a result of steric effects. The results also show that the formation of cation-π interactions between Arg and Phe depends on their relative positions in the strand. Moreover, the fluorinated and methylated Phe substitutions show that an electron-withdrawing or electron-donating substituent on the aromatic ring can modulate its π-electron density and the cation-π interaction in collagen. Our data demonstrate that the cation-π interaction could play an important role in stabilizing the collagen triple helix.

  8. Competition between kaolinite flocculation and stabilization in divalent cation solutions dosed with anionic polyacrylamides. (United States)

    Lee, Byung Joon; Schlautman, Mark A; Toorman, Erik; Fettweis, Michael


    Divalent cations have been reported to develop bridges between anionic polyelectrolytes and negatively-charged colloidal particles, thereby enhancing particle flocculation. However, results from this study of kaolinite suspensions dosed with various anionic polyacrylamides (PAMs) reveal that Ca(2+) and Mg(2+) can lead to colloid stabilization under some conditions. To explain the opposite but coexisting processes of flocculation and stabilization with divalent cations, a conceptual flocculation model with (1) particle-binding divalent cationic bridges between PAM molecules and kaolinite particles and (2) polymer-binding divalent cationic bridges between PAM molecules is proposed. The particle-binding bridges enhanced flocculation and aggregated kaolinite particles in large, easily-settleable flocs whereas the polymer-binding bridges increased steric stabilization by developing polymer layers covering the kaolinite surface. Both the particle-binding and polymer-binding divalent cationic bridges coexist in anionic PAM- and kaolinite-containing suspensions and thus induce the counteracting processes of particle flocculation and stabilization. Therefore, anionic polyelectrolytes in divalent cation-enriched aqueous solutions can sometimes lead to the stabilization of colloidal particles due to the polymer-binding divalent cationic bridges.

  9. Quantitative characterization of non-classic polarization of cations on clay aggregate stability.

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    Feinan Hu

    Full Text Available Soil particle interactions are strongly influenced by the concentration, valence and ion species and the pH of the bulk solution, which will also affect aggregate stability and particle transport. In this study, we investigated clay aggregate stability in the presence of different alkali ions (Li+, Na+, K+, and Cs+ at concentrations from10-5 to 10-1 mol L-1. Strong specific ion effects on clay aggregate stability were observed, and showed the order Cs+>K+>Na+>Li+. We found that it was not the effects of ion size, hydration, and dispersion forces in the cation-surface interactions but strong non-classic polarization of adsorbed cations that resulted in these specific effects. In this study, the non-classic dipole moments of each cation species resulting from the non-classic polarization were estimated. By comparing non-classic dipole moments with classic values, the observed dipole moments of adsorbed cations were up to 104 times larger than the classic values for the same cation. The observed non-classic dipole moments sharply increased with decreasing electrolyte concentration. We conclude that strong non-classic polarization could significantly suppress the thickness of the diffuse layer, thereby weakening the electric field near the clay surface and resulting in improved clay aggregate stability. Even though we only demonstrated specific ion effects on aggregate stability with several alkali ions, our results indicate that these effects could be universally important in soil aggregate stability.

  10. Switchable Pickering emulsions stabilized by silica nanoparticles hydrophobized in situ with a conventional cationic surfactant. (United States)

    Zhu, Yue; Jiang, Jianzhong; Liu, Kaihong; Cui, Zhenggang; Binks, Bernard P


    A stable oil-in-water Pickering emulsion stabilized by negatively charged silica nanoparticles hydrophobized in situ with a trace amount of a conventional cationic surfactant can be rendered unstable on addition of an equimolar amount of an anionic surfactant. The emulsion can be subsequently restabilized by adding a similar trace amount of cationic surfactant along with rehomogenization. This destabilization-stabilization behavior can be cycled many times, demonstrating that the Pickering emulsion is switchable. The trigger is the stronger electrostatic interaction between the oppositely charged ionic surfactants compared with that between the cationic surfactant and the (initially) negatively charged particle surfaces. The cationic surfactant prefers to form ion pairs with the added anionic surfactant and thus desorbs from particle surfaces rendering them surface-inactive. This access to switchable Pickering emulsions is easier than those employing switchable surfactants, polymers, or surface-active particles, avoiding both the complicated synthesis and the stringent switching conditions.

  11. Cationic and radical intermediates in the acid photorelease from aryl sulfonates and phosphates. (United States)

    Terpolilli, Marco; Merli, Daniele; Protti, Stefano; Dichiarante, Valentina; Fagnoni, Maurizio; Albini, Angelo


    The irradiation of a series of phenyl sulfonates and phosphates leads to the quantitative release of acidity with a reasonable quantum yield (≈0.2). Products characterization, ion chromatography analysis and potentiometric titration are consistent with the intervening of two different paths in this reaction, viz. cationic with phosphates and (mainly) radical with sulfonates.

  12. An expedient synthesis of functionalized 1,4-diketone-derived compounds via silyloxyallyl cation intermediates. (United States)

    Stepherson, Jacob R; Fronczek, Frank R; Kartika, Rendy


    Herein we describe a new method, enabling the synthesis of highly functionalized 1,4-diketones that are readily differentiated as monosilylenol ethers under Brønsted acid catalysis. This synthetically useful chemistry exploited an intermediacy of unsymmetrical silyloxyallyl cations, which were directly captured by silyl enolates to create the targeted α,α carbon-carbon linkages in a regioselective manner. Our reaction conditions proved to be mild, rendering the silylenol ether functionalities intact.

  13. Synthesis of linear and cyclic peptide-PEG-lipids for stabilization and targeting of cationic liposome-DNA complexes. (United States)

    Ewert, Kai K; Kotamraju, Venkata Ramana; Majzoub, Ramsey N; Steffes, Victoria M; Wonder, Emily A; Teesalu, Tambet; Ruoslahti, Erkki; Safinya, Cyrus R


    Because nucleic acids (NAs) have immense potential value as therapeutics, the development of safe and effective synthetic NA vectors continues to attract much attention. In vivo applications of NA vectors require stabilized, nanometer-scale particles, but the commonly used approaches of steric stabilization with a polymer coat (e.g., PEGylation; PEG=poly(ethylene glycol)) interfere with attachment to cells, uptake, and endosomal escape. Conjugation of peptides to PEG-lipids can improve cell attachment and uptake for cationic liposome-DNA (CL-DNA) complexes. We present several synthetic approaches to peptide-PEG-lipids and discuss their merits and drawbacks. A lipid-PEG-amine building block served as the common key intermediate in all synthetic routes. Assembling the entire peptide-PEG-lipid by manual solid phase peptide synthesis (employing a lipid-PEG-carboxylic acid) allowed gram-scale synthesis but is mostly applicable to linear peptides connected via their N-terminus. Conjugation via thiol-maleimide or strain-promoted (copper-free) azide-alkyne cycloaddition chemistry is highly amenable to on-demand preparation of peptide-PEG-lipids, and the appropriate PEG-lipid precursors are available in a single chemical step from the lipid-PEG-amine building block. Azide-alkyne cycloaddition is especially suitable for disulfide-bridged peptides such as iRGD (cyclic CRGDKGPDC). Added at 10 mol% of a cationic/neutral lipid mixture, the peptide-PEG-lipids stabilize the size of CL-DNA complexes. They also affect cell attachment and uptake of nanoparticles in a peptide-dependent manner, thereby providing a platform for preparing stabilized, affinity-targeted CL-DNA nanoparticles.

  14. Storage Stability and Improvement of Intermediate Moisture Foods (United States)

    Labuza, T. P.


    Shelf life tests are used to estimate the rate of nonenzymatic browning; however, controlling the reducing sugar levels below 23:1 molar ratio to amines, slows the rate. In addition, liquid glycols surpress browning. The protozoan Tetrahymena pyriformis W can be used to estimate nutrition losses during browning. At high temperatures (80 to 120 C) used in processing intermediate moisture foods (IMF), vitamin C destruction shifts to a zero order mechanism. BHA and BHT are the most effective antioxidants against rancidity. In shelf life testing however, 45 C should be the maximum temperature used. Water binding agents are studied. The five isotherms of thirteen humectants were determined. The results show that neither the method of addition nor sequence of addition affects the a sub u lowering ability of these humectants. Results were used to formulate shelf stable IMF processed cheese foods with at least four months shelf life.

  15. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface (United States)

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; Crumlin, Ethan J.; Yildiz, Bilge


    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a `volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.


    Institute of Scientific and Technical Information of China (English)

    Xiao-ping Yan; Bao-lin He; Jie Zhang; Han-fan Liu


    Modification of transition metal cations to polymer-stabilized Pt colloidal clusters modified with cinchonidine was studied in enantioselective hydrogenation of methyl pyruvate. Compared to the enantiomeric excess (e.e.) value (71.4%)obtained without the presence of metal cations, obvious e.e. enhancement (up to 82.5%) was resulted from the addition of Zn2+ but with a certain decrease in activity. The reaction parameters in the presence of Zn2+ were also studied. It was found that the Pt colloidal catalysts in the presence of metal cations performed very differently from that in the absence of metal cations.

  17. On the Stability of an Intermediate Coupled Ocean-Atmosphere Model

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    Tianxu Zhao


    Full Text Available The explicit finite difference scheme for solving an intermediate coupled ocean-atmosphere equations has been proposed and discussed. The discrete Fourier analysis within Gerschgorin circle theorem is applied to the stability analysis of this numerical model. The stability criterion that we obtained includes advection, rotation, dissipation, and friction terms, without any assumptions, which is also including the Courant-Friedrichs-Lewy (CFL condition as a special case. Numerical sensitivity experiments are also carried out by varying the model parameters.

  18. Alkaline stability of quaternary ammonium cations for alkaline fuel cell membranes and ionic liquids. (United States)

    Marino, M G; Kreuer, K D


    The alkaline stability of 26 different quaternary ammonium groups (QA) is investigated for temperatures up to 160 °C and NaOH concentrations up to 10 mol L(-1) with the aim to provide a basis for the selection of functional groups for hydroxide exchange membranes in alkaline fuel cells and of ionic-liquid cations stable in basic conditions. Most QAs exhibit unexpectedly high alkaline stability with the exception of aromatic cations. β-Protons are found to be far less susceptible to nucleophilic attack than previously suggested, whereas the presence of benzyl groups, nearby hetero-atoms, or other electron-withdrawing species promote degradation reactions significantly. Cyclic QAs proved to be exceptionally stable, with the piperidine-based 6-azonia-spiro[5.5]undecane featuring the highest half-life at the chosen conditions. Absolute and relative stabilities presented herein stand in contrast to literature data, the differences being ascribed to solvent effects on degradation.

  19. Graphene Oxide Nanofiltration Membranes Stabilized by Cationic Porphyrin for High Salt Rejection. (United States)

    Xu, Xiao-Ling; Lin, Fu-Wen; Du, Yong; Zhang, Xi; Wu, Jian; Xu, Zhi-Kang


    Swelling has great influences on the structure stability and separation performance of graphene oxide laminate membranes (GOLMs) for water desalination and purification. Herein, we report cross-linked GOLMs from GO assembled with cationic tetrakis(1-methyl-pyridinium-4-yl)porphyrin (TMPyP) by a vacuum-assisted strategy. The concave nonoxide regions (G regions) of GO are used as cross-linking sites for the first time to precisely control the channel size for water permeation and salt ion retention. Channels around 1 nm are constructed by modulating the assembly ratio of TMPyP/GO, and these cross-linked GOLMs show high salt rejection.

  20. Fluorescence behavior of cis-methyl orange stabilized in cationic premicelles. (United States)

    Dutta, Anisha; Dutta, Robin K


    The cis-isomer of methyl orange (MO), stabilized in cationic premicelles, has been found to be fluorescence active when excited at wavelength ≤270nm. An intense fluorescence band with maximum at 575nm along with a broad moderate intensity band in the range of 370-530nm and a low intensity band at 361nm have been observed. The major band at 575nm has been attributed to S1→S0 (n-π(*)) fluorescence unlike the other azobenzenes where the S2→S0 (π-π(*)) fluorescence is usually reported. UV-Vis spectral and surface tension study indicate that the dye exists in the trans form in dye-surfactant ionpair (DSIP) at very dilute concentrations of the surfactant. But the polar cis-isomer is stabilized by micellization of the DSIPs as the concentration of the surfactant is increased. The fluorescence and hence the cis-isomer again disappear when normal micelles are formed above the normal CMC of the surfactant. It has been suggested that the symmetry forbidden S1→S0 (n-π(*)) transition of MO becomes allowed due to the formation of the twisted cis-form. TD-DFT calculations have been used as an auxiliary tool to identify the possible structures and electronic transitions responsible for the specific absorption and fluorescence properties of MO observed in presence of premicellar cationic surfactants.

  1. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    NARCIS (Netherlands)

    Drayss, M. K.; Armentrout, P. B.; Oomens, J.; Schaefer, M.


    Gas-phase structures of alkali metal cationized (Li+, Na+,K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD spectra

  2. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    NARCIS (Netherlands)

    Drayß, M.K.; Armentrout, P.B.; Oomens, J.; Schäfer, M.


    Gas-phase structures of alkali metal cationized (Li+, Na+, K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD spectr

  3. Effects of polyols on the stability of whey proteins in intermediate-moisture food model systems. (United States)

    Liu, Xiaoming; Zhou, Peng; Tran, Amy; Labuza, Ted P


    The objective of this study was to investigate the influence of polyols on the stability of whey proteins in an intermediate-moisture food model system and to elucidate the effect of polyols on the hardening of whey protein-based bars during storage. Four major polyols, glycerol, propylene glycol, maltitol, and sorbitol, were evaluated in model systems, which contained whey protein isolate, polyols, and water. The results showed that glycerol was the most effective polyol in lowering water activity and provided the soft texture of intermediate-moisture foods, followed by sorbitol and maltitol. These three polyols stabilized the native structure of whey proteins, provided a desired texture, and slowed the hardening of the model systems. Propylene glycol should not be used in whey protein-based high-protein intermediate-moisture foods because it caused changes in protein conformation and stability as observed by differential scanning calorimeter and Fourier transform infrared spectroscopy and resulted in aggregation of whey proteins and hardening of the bar texture during storage, causing loss in product quality.

  4. Understanding the Cubic Phase Stabilization and Crystallization Kinetics in Mixed Cations and Halides Perovskite Single Crystals. (United States)

    Xie, Li-Qiang; Chen, Liang; Nan, Zi-Ang; Lin, Hai-Xin; Wang, Tan; Zhan, Dong-Ping; Yan, Jia-Wei; Mao, Bing-Wei; Tian, Zhong-Qun


    The spontaneous α-to-δ phase transition of the formamidinium-based (FA) lead halide perovskite hinders its large scale application in solar cells. Though this phase transition can be inhibited by alloying with methylammonium-based (MA) perovskite, the underlying mechanism is largely unexplored. In this Communication, we grow high-quality mixed cations and halides perovskite single crystals (FAPbI3)1-x(MAPbBr3)x to understand the principles for maintaining pure perovskite phase, which is essential to device optimization. We demonstrate that the best composition for a perfect α-phase perovskite without segregation is x = 0.1-0.15, and such a mixed perovskite exhibits carrier lifetime as long as 11.0 μs, which is over 20 times of that of FAPbI3 single crystal. Powder XRD, single crystal XRD and FT-IR results reveal that the incorporation of MA(+) is critical for tuning the effective Goldschmidt tolerance factor toward the ideal value of 1 and lowering the Gibbs free energy via unit cell contraction and cation disorder. Moreover, we find that Br incorporation can effectively control the perovskite crystallization kinetics and reduce defect density to acquire high-quality single crystals with significant inhibition of δ-phase. These findings benefit the understanding of α-phase stabilization behavior, and have led to fabrication of perovskite solar cells with highest efficiency of 19.9% via solvent management.

  5. Elucidating the Higher Stability of Vanadium (V) Cations in Mixed Acid Based Redox Flow Battery Electrolytes

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    Vijayakumar, M.; Wang, Wei; Nie, Zimin; Sprenkle, Vincent L.; Hu, Jian Z.


    The Vanadium (V) cation structures in mixed acid based electrolyte solution were analysed by density functional theory (DFT) based computational modelling and 51V and 35Cl Nuclear Magnetic Resonance (NMR) spectroscopy. The Vanadium (V) cation exists as di-nuclear [V2O3Cl2.6H2O]2+ compound at higher vanadium concentrations (≥1.75M). In particular, at high temperatures (>295K) this di-nuclear compound undergoes ligand exchange process with nearby solvent chlorine molecule and forms chlorine bonded [V2O3Cl2.6H2O]2+ compound. This chlorine bonded [V2O3Cl2.6H2O]2+ compound might be resistant to the de-protonation reaction which is the initial step in the precipitation reaction in Vanadium based electrolyte solutions. The combined theoretical and experimental approach reveals that formation of chlorine bonded [V2O3Cl2.6H2O]2+ compound might be central to the observed higher thermal stability of mixed acid based Vanadium (V) electrolyte solutions.

  6. Stability of A Coevolving Host-parasite System Peaks at Intermediate Productivity (United States)

    Zhao, Xin-Feng; Hao, Yi-Qi; Zhang, Quan-Guo


    Habitat productivity may affect the stability of consumer-resource systems, through both ecological and evolutionary mechanisms. We hypothesize that coevolving consumer-resource systems show more stable dynamics at intermediate resource availability, while very low-level resource supply cannot support sufficiently large populations of resource and consumer species to avoid stochastic extinction, and extremely resource-rich environments may promote escalatory arms-race-like coevolution that can cause strong fluctuations in species abundance and even extinction of one or both trophic levels. We tested these ideas by carrying out an experimental evolution study with a model bacterium-phage system (Pseudomonas fluorescens SBW25 and its phage SBW25Φ2). Consistent with our hypothesis, this system was most stable at intermediate resource supply (fewer extinction events and smaller magnitude of population fluctuation). In our experiment, the rate of coevolution between bacterial resistance and phage infectivity was correlated with the magnitude of population fluctuation, which may explain the different in stability between levels of resource supply. Crucially, our results are consistent with a suggestion that, among the two major modes of antagonistic coevolution, arms race is more likely than fluctuation selection dynamics to cause extinction events in consumer-resource systems. This study suggests an important role of environment-dependent coevolutionary dynamics for the stability of consumer-resource species systems, therefore highlights the importance to consider contemporaneous evolutionary dynamics when studying the stability of ecosystems, particularly those under environmental changes. PMID:28076419

  7. Chitosan based atorvastatin nanocrystals: effect of cationic charge on particle size, formulation stability, and in-vivo efficacy

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    Kurakula M


    Full Text Available Mallesh Kurakula,1 AM El-Helw,2 Tariq R Sobahi,1 Magdy Y Abdelaal11Polymer Research Lab, Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia; 2Department of Pharmaceutics, Faculty of Pharmacy, King Abdulaziz University, Jeddah, Saudi ArabiaAbstract: Cationic charged chitosan as stabilizer was evaluated in preparation of nanocrystals using probe sonication method. The influence of cationic charge densities of chitosan (low CSL, medium CSM, high CSH molecular weights and Labrasol® in solubility enhancement and modifying the release was investigated, using atorvastatin (ATR as poorly soluble model drug. Compared to CSM and CSH; low cationic charge of CSL acted as both electrostatic and steric stabilizer by significant size reduction to 394 nm with charge of 21.5 meV. Solubility of ATR-CSL increased to 60-fold relative to pure ATR and ATR-L. Nanocrystals were characterized for physiochemical properties. Scanning electron microscopy revealed scaffold-like structures with high surface area. X-ray powder diffractometry and differential scanning calorimetry revealed crystalline to slight amorphous state changes after cationic charge size reduction. Fourier transform-infrared spectra indicated no potent drug-excipient interactions. The enhanced dissolution profile of ATR-CSL indicates that sustained release was achieved compared with ATR-L and Lipitor®. Anti-hyperlipidemic performance was pH dependent where ATR-CSL exhibited 2.5-fold higher efficacy at pH 5 compared to pH 6 and Lipitor®. Stability studies indicated marked changes in size and charge for ATR-L compared to ATR-CSL exemplifying importance of the stabilizer. Therefore, nanocrystals developed with CSL as a stabilizer is a promising choice to enhance dissolution, stability, and in-vivo efficacy of major Biopharmaceutical Classification System II/IV drugs.Keywords: atorvastatin, anti-hyperlipidemia, chitosan, cationic charge, stability, nanocrystals

  8. Impact assessment of intermediate soil cover on landfill stabilization by characterizing landfilled municipal solid waste. (United States)

    Qi, Guangxia; Yue, Dongbei; Liu, Jianguo; Li, Rui; Shi, Xiaochong; He, Liang; Guo, Jingting; Miao, Haomei; Nie, Yongfeng


    Waste samples at different depths of a covered municipal solid waste (MSW) landfill in Beijing, China, were excavated and characterized to investigate the impact of intermediate soil cover on waste stabilization. A comparatively high amount of unstable organic matter with 83.3 g kg(-1) dry weight (dw) total organic carbon was detected in the 6-year-old MSW, where toxic inorganic elements containing As, Cd, Cr, Cu, Mn, Ni, Pb, and Zn of 10.1, 0.98, 85.49, 259.7, 530.4, 30.5, 84.0, and 981.7 mg kg(-1) dw, respectively, largely accumulated because of the barrier effect of intermediate soil cover. This accumulation resulted in decreased microbial activities. The intermediate soil cover also caused significant reduction in moisture in MSW under the soil layer, which was as low as 25.9%, and led to inefficient biodegradation of 8- and 10-year-old MSW. Therefore, intermediate soil cover with low permeability seems to act as a barrier that divides a landfill into two landfill cells with different degradation processes by restraining water flow and hazardous matter.

  9. Oms1 associates with cytochrome c oxidase assembly intermediates to stabilize newly synthesized Cox1. (United States)

    Bareth, Bettina; Nikolov, Miroslav; Lorenzi, Isotta; Hildenbeutel, Markus; Mick, David U; Helbig, Christin; Urlaub, Henning; Ott, Martin; Rehling, Peter; Dennerlein, Sven


    The mitochondrial cytochrome c oxidase assembles in the inner membrane from subunits of dual genetic origin. The assembly process of the enzyme is initiated by membrane insertion of the mitochondria-encoded Cox1 subunit. During complex maturation, transient assembly intermediates, consisting of structural subunits and specialized chaperone-like assembly factors, are formed. In addition, cofactors such as heme and copper have to be inserted into the nascent complex. To regulate the assembly process, the availability of Cox1 is under control of a regulatory feedback cycle in which translation of COX1 mRNA is stalled when assembly intermediates of Cox1 accumulate through inactivation of the translational activator Mss51. Here we isolate a cytochrome c oxidase assembly intermediate in preparatory scale from coa1Δ mutant cells, using Mss51 as bait. We demonstrate that at this stage of assembly, the complex has not yet incorporated the heme a cofactors. Using quantitative mass spectrometry, we define the protein composition of the assembly intermediate and unexpectedly identify the putative methyltransferase Oms1 as a constituent. Our analyses show that Oms1 participates in cytochrome c oxidase assembly by stabilizing newly synthesized Cox1.

  10. Upward and downward comparison in the intermediate-status group: the role of social stratification stability. (United States)

    Caricati, Luca


    This work analyses intergroup comparison choices made by intermediate-status group members. Seventy-six psychology students were categorized in an intermediate position with respect to other faculties. Stability was manipulated at three levels: stable, upwardly unstable, and downwardly unstable. Data on strength of comparison, comparison for enhancing, comparison for evaluation, and ingroup identification were collected. Results revealed that in the stable condition, participants were equally engaged in both upward and downward comparison. In the upwardly unstable condition, participants were more likely to compare themselves with the high-status group, whereas in the downwardly unstable condition, they were more likely to choose a downward comparison. In this latter condition, both downward comparison for enhancement and in-group identification were lower than in other conditions.

  11. Nanocomplexation of thrombin with cationic amylose derivative for improved stability and hemostatic efficacy

    Directory of Open Access Journals (Sweden)

    Zhuang B


    Full Text Available Baoxiong Zhuang,1,* Zhihua Li,1,* Jiadong Pang,2,* Wenbin Li,1 Pinbo Huang,1 Jie Wang,1 Yu Zhou,1 Qing Lin,1 Quanbo Zhou,1 Xiao Ye,1 Huilin Ye,1 Yimin Liu,1 Li-Ming Zhang,2 Rufu Chen1 1Department of Hepato-Pancreato-Billiary Surgery, Department of Medical Oncology, Sun Yat-sen Memorial Hospital, Sun Yat-sen University, Guangzhou, People’s Republic of China; 2DSAPM Lab and PCFM Lab, Institute of Polymer Science, Department of Polymer and Materials Science, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou, People’s Republic of China *Authors share co-first authorship Abstract: As a topical hemostatic agent, thrombin has wide application for many surgical treatments. However, native thrombin always suffers from its physical and chemical instabilities. In this work, a nanocomplexation strategy was developed for modifying the stability and hemostatic efficacy of thrombin, in which a water-soluble cationic amylose derivative containing poly(l-lysine dendrons was prepared by a click reaction and then used to complex thrombin in an aqueous system. For resultant thrombin nanocomplexes, their morphology and particle size distribution were investigated. Their stabilities were studied in terms of activity retention percentages under different storage time, pH values, and illumination time. In addition, their ability to achieve in vitro fibrinogen and blood coagulation were evaluated. Via a rat hepatic hemorrhage model and a rat iliac artery hemorrhage model, these thrombin nanocomplexes were confirmed to have good tissue biocompatibility and in vivo hemostatic effectiveness. Keywords: thrombin, nanoparticles, amylose derivative, complexation, stability, hemostatic activity

  12. Stabilization of cationic and anionic metal species in contaminated soils using sludge-derived biochar. (United States)

    Fang, Shen'en; Tsang, Daniel C W; Zhou, Fengsha; Zhang, Weihua; Qiu, Rongliang


    Currently, sludge pyrolysis has been considered as a promising technology to solve disposal problem of municipal sewage sludge, recover sludge heating value, sequester carbon and replenish nutrients in farmland soils. The resultant sludge-derived biochar (SDBC) is potentially an excellent stabilizing agent for metal species. This study applied the SDBC into four soils that had been contaminated in field with cationic Pb(II) and Cd(II)/Ni(II), and anionic Cr(VI) and As(III), respectively. The performance of metal stabilization under various operational and environmental conditions was evaluated with acid batch extraction and column leaching tests. Results indicated the SDBC could effectively stabilize these metals, which was favored by elevated temperature and longer aging. Periodic temperature decrease from 45 to 4 °C resulted in the release of immobilized Cr(VI) and As(III) but not Pb(II). However, a longer aging time offset such metal remobilization. This was possibly because more Pb was strongly bound and even formed stable precipitates, as shown by XRD and sequential extraction results. With increasing time, Cr(VI) was sorbed and partly reduced to Cr(III), while immobilized As(III) was co-oxidized to As(V) as indicated by XPS spectra. Column tests revealed that adding SDBC as a separate layer was unfavorable because the concentrated Cd(II) and Ni(II) in localized positions increased the peak levels of metal release under continuous acid leaching. In contrast, uniformly mixed SDBC could effectively delay the metal breakthrough and reduce their released amounts. Yet, a long-term monitoring may be required for evaluating the potential leaching risks and bioavailability/toxicity of these immobilized and transformed species in the SDBC-amended soils.

  13. Preparation, stability and antimicrobial activity of cationic cross-linked starch-iodine complexes. (United States)

    Klimaviciute, Rima; Bendoraitiene, Joana; Rutkaite, Ramune; Siugzdaite, Jurate; Zemaitaitis, Algirdas


    Cationic cross-linked starch (CCS)-iodine complexes containing different amounts of quaternary ammonium groups (different degrees of substitution (DS)) and iodine have been obtained by iodine adsorption on CCS from aqueous iodine potassium iodide solution. Equilibrium adsorption studies showed that with an increase of DS the amount of iodine adsorbed on CCS and the affinity of iodine to CCS increased linearly. The influences of the DS of CCS and the amount of adsorbed iodine on the stability of CCS-iodine complexes in a solution of 0.02M sodium acetate and reactivity toward l-tyrosine have been investigated. At the same DS, the stability of CCS-iodine complexes decreased with an increase of the amount of adsorbed iodine. With increasing the DS, the stability of CCS-iodine complexes increased. The iodine consumption in the reaction with l-tyrosine increased significantly with an increase of the amount of adsorbed iodine. The influence of DS on iodine consumption was lower and depended on the amount of adsorbed iodine. The antibacterial activity of CCS-iodine complexes against Bacillus cereus, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli was determined by the broth-dilution and spread-plate methods. The obtained results have demonstrated that an appropriate selection of the CCS-iodine complex composition (the DS of CCS and the amount of adsorbed iodine) could ensure good antimicrobial properties by keeping a low concentration of free iodine in the system. The main advantage of using CCS-iodine complexes as antimicrobial agents is the biodegradability of the polymeric matrix.

  14. Decoding the folding of Burkholderia glumae lipase: folding intermediates en route to kinetic stability.

    Directory of Open Access Journals (Sweden)

    Kris Pauwels

    Full Text Available The lipase produced by Burkholderia glumae folds spontaneously into an inactive near-native state and requires a periplasmic chaperone to reach its final active and secretion-competent fold. The B. glumae lipase-specific foldase (Lif is classified as a member of the steric-chaperone family of which the propeptides of α-lytic protease and subtilisin are the best known representatives. Steric chaperones play a key role in conferring kinetic stability to proteins. However, until present there was no solid experimental evidence that Lif-dependent lipases are kinetically trapped enzymes. By combining thermal denaturation studies with proteolytic resistance experiments and the description of distinct folding intermediates, we demonstrate that the native lipase has a kinetically stable conformation. We show that a newly discovered molten globule-like conformation has distinct properties that clearly differ from those of the near-native intermediate state. The folding fingerprint of Lif-dependent lipases is put in the context of the protease-prodomain system and the comparison reveals clear differences that render the lipase-Lif systems unique. Limited proteolysis unveils structural differences between the near-native intermediate and the native conformation and sets the stage to shed light onto the nature of the kinetic barrier.

  15. Stability of Perovskite Solar Cells: A Prospective on the Substitution of the A Cation and X Anion. (United States)

    Wang, Ze; Shi, Zejiao; Li, Taotao; Chen, Yonghua; Huang, Wei


    In recent years, organometal trihalide perovskites have emerged as promising materials for low-cost, flexible, and highly efficient solar cells. Despite their processing advantages, before the technology can be commercialized the poor stability of the organic-inorganic hybrid perovskite materials with regard to humidity, heat, light, and oxygen has be to overcome. Herein, we distill the current state-of-the-art and highlight recent advances in improving the chemical stability of perovskite materials by substitution of the A-cation and X-anion. Our hope is to pave the way for the rational design of perovskite materials to realize perovskite solar cells with unprecedented improvement in stability.

  16. Cation and anion dependence of stable geometries and stabilization energies of alkali metal cation complexes with FSA(-), FTA(-), and TFSA(-) anions: relationship with physicochemical properties of molten salts. (United States)

    Tsuzuki, Seiji; Kubota, Keigo; Matsumoto, Hajime


    Stable geometries and stabilization energies (Eform) of the alkali metal complexes with bis(fluorosulfonyl)amide, (fluorosulfonyl)(trifluoromethylslufonyl)amide and bis(trifluoromethylsulfonyl)amide (FSA(-), FTA(-) and TFSA(-)) were studied by ab initio molecular orbital calculations. The FSA(-) complexes prefer the bidentate structures in which two oxygen atoms of two SO2 groups have contact with the metal cation. The FTA(-) and TFSA(-) complexes with Li(+) and Na(+) prefer the bidentate structures, while the FTA(-) and TFSA(-) complexes with Cs(+) prefer tridentate structures in which the metal cation has contact with two oxygen atoms of an SO2 group and one oxygen atom of another SO2 group. The two structures are nearly isoenergetic in the FTA(-) and TFSA(-) complexes with K(+) and Rb(+). The magnitude of Eform depends on the alkali metal cation significantly. The Eform calculated for the most stable TFSA(-) complexes with Li(+), Na(+), K(+), Rb(+) and Cs(+) cations at the MP2/6-311G** level are -137.2, -110.5, -101.1, -89.6, and -84.1 kcal/mol, respectively. The viscosity and ionic conductivity of the alkali TFSA molten salts have strong correlation with the magnitude of the attraction. The viscosity increases and the ionic conductivity decreases with the increase of the attraction. The melting points of the alkali TFSA and alkali BETA molten salts also have correlation with the magnitude of the Eform, which strongly suggests that the magnitude of the attraction play important roles in determining the melting points of these molten salts. The anion dependence of the Eform calculated for the complexes is small (less than 2.9 kcal/mol). This shows that the magnitude of the attraction is not the cause of the low melting points of alkali FTA molten salts compared with those of corresponding alkali TFSA molten salts. The electrostatic interactions are the major source of the attraction in the complexes. The electrostatic energies for the most stable TFSA

  17. Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III Reaction Intermediate Models of Peroxidase Enzymes

    Directory of Open Access Journals (Sweden)

    Samuel Hernández Anzaldo


    Full Text Available The spectroscopic and kinetic characterization of two intermediates from the H2O2 oxidation of three dimethyl ester [(proto, (meso, (deuteroporphyrinato (picdien]Fe(III complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III quantum mixed spin (qms ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1–3 + guaiacol + H2O2 → oxidation guaiacol products. The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III and H2O2, resulting in only two types of kinetics that were developed during the first 0–4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III family with the ligand picdien [N,N’-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, 1H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

  18. Ionic and Covalent Stabilization of Intermediates and Transition States in Catalysis by Solid Acids

    Energy Technology Data Exchange (ETDEWEB)

    Deshlahra, Prashant; Carr, Robert T.; Iglesia, Enrique


    Reactivity descriptors describe catalyst properties that determine the stability of kinetically relevant transition states and adsorbed intermediates. Theoretical descriptors, such as deprotonation energies (DPE), rigorously account for Brønsted acid strength for catalytic solids with known structure. Here, mechanistic interpretations of methanol dehydration turnover rates are used to assess how charge reorganization (covalency) and electrostatic interactions determine DPE and how such interactions are recovered when intermediates and transition states interact with the conjugate anion in W and Mo polyoxometalate (POM) clusters and gaseous mineral acids. Turnover rates are lower and kinetically relevant species are less stable on Mo than W POM clusters with similar acid strength, and such species are more stable on mineral acids than that predicted from W-POM DPE–reactivity trends, indicating that DPE and acid strength are essential but incomplete reactivity descriptors. Born–Haber thermochemical cycles indicate that these differences reflect more effective charge reorganization upon deprotonation of Mo than W POM clusters and the much weaker reorganization in mineral acids. Such covalency is disrupted upon deprotonation but cannot be recovered fully upon formation of ion pairs at transition states. Predictive descriptors of reactivity for general classes of acids thus require separate assessments of the covalent and ionic DPE components. Here, we describe methods to estimate electrostatic interactions, which, taken together with energies derived from density functional theory, give the covalent and ionic energy components of protons, intermediates, and transition states. In doing so, we provide a framework to predict the reactive properties of protons for chemical reactions mediated by ion-pair transition states.

  19. Ionic and covalent stabilization of intermediates and transition states in catalysis by solid acids. (United States)

    Deshlahra, Prashant; Carr, Robert T; Iglesia, Enrique


    Reactivity descriptors describe catalyst properties that determine the stability of kinetically relevant transition states and adsorbed intermediates. Theoretical descriptors, such as deprotonation energies (DPE), rigorously account for Brønsted acid strength for catalytic solids with known structure. Here, mechanistic interpretations of methanol dehydration turnover rates are used to assess how charge reorganization (covalency) and electrostatic interactions determine DPE and how such interactions are recovered when intermediates and transition states interact with the conjugate anion in W and Mo polyoxometalate (POM) clusters and gaseous mineral acids. Turnover rates are lower and kinetically relevant species are less stable on Mo than W POM clusters with similar acid strength, and such species are more stable on mineral acids than that predicted from W-POM DPE-reactivity trends, indicating that DPE and acid strength are essential but incomplete reactivity descriptors. Born-Haber thermochemical cycles indicate that these differences reflect more effective charge reorganization upon deprotonation of Mo than W POM clusters and the much weaker reorganization in mineral acids. Such covalency is disrupted upon deprotonation but cannot be recovered fully upon formation of ion pairs at transition states. Predictive descriptors of reactivity for general classes of acids thus require separate assessments of the covalent and ionic DPE components. Here, we describe methods to estimate electrostatic interactions, which, taken together with energies derived from density functional theory, give the covalent and ionic energy components of protons, intermediates, and transition states. In doing so, we provide a framework to predict the reactive properties of protons for chemical reactions mediated by ion-pair transition states.

  20. The Linear Stability of the Responses of Axially Moving Beams Supported by an Intermediate Spring

    Directory of Open Access Journals (Sweden)

    Kostekci F.


    Full Text Available In the present paper, the stability investigation of the linear responses of axially travelling beams supported by an intermediate linear spring is performed numerically by means of searching linear complex eigenvalues. The boundary conditions and the dynamic equation of motion are obtained by means of the Extended Principle of Hamilton for the two-span Euler-Bernoulli beam. Assuming the harmonic solution of the governing differential equations of motion, the dispersion relation is derived. To have a nontrivial solution in conjunction with the dispersion relation, the frequency equation is obtained by letting the determinant of the matrix representing the coefficients of the equations of the boundary conditions be equal to zero. The aim of this contribution is to compute the complex values of the natural frequencies from the nonlinear frequency equation by means of numerical methods for the beam supported by an intermediate spring. The real and imaginary parts of the complex eigenvalues versus the constant axial transport speed curves are depicted in order to show the linear instability. Depending on the signs of the real and imaginary parts of the complex eigenvalues, the boundaries of the instability regions were observed.

  1. Aggregation and Stability of Reduced Graphene Oxide: Complex Roles of Divalent Cations, pH, and Natural Organic Matter (United States)

    The aggregation and stability of graphene oxide (GO) and three successively reduced GO (rGO) nanomaterials were investigated. Reduced GO species were partially reduced GO (rGO-1h), intermediately reduced GO (rGO-2h), and fully reduced GO (rGO-5h). Specifically, influence of pH, i...

  2. Observation of Transient Surface-Bound Intermediates by Interfacial Matrix Stabilization Spectroscopy (imss) (United States)

    Jarrah, Nina K.; Moore, David T.


    Interfacial matrix stabilization spectroscopy is a new technique based on matrix isolation spectroscopy, but where a cryogenic matrix is deposited over the top of a film sample, in order to characterize interactions between the substrate and molecular dopants. The IMSS technique harnesses the well-established ability of cryogenic matrices to trap and stabilize transient species, although in this case it is applied to intermediates relevant to heterogeneous catalysis. In this proof-of-concept study, we present data for CO and O2 reactants binding to TiO2 and Au/TiO2 nanoparticle films, where in the latter case the Au nanoparticles were created by de-wetting of a 22.5 nm overlayer at 450 K. The films are first pre-saturated with CO at 40 K, then cooled to 20 K, at which point an argon matrix is deposited over the top of them. The spectra are then annealed in stages over a range of temperatures between 20 and 40 K. In all cases, the presence of the Ar matrix alters the appearance of the CO bands, revealing additional structure, such as a broad feature at 2150 wn, which is typically attributed to CO interacting with OH groups on the TiO2 surface, but is not observed at 40 K for these samples in the absence of the matrix. The interpretation is that the matrix induces a caging-effect that prevents molecules from desorbing from weak binding sites from which they would be "pumped away" in the vacuum chamber if the matrix were not present. Perhaps the most interesting feature of these spectra is a small but sharp band at 2112 wn that appears ONLY when O2 is added to the argon matrix as a dopant. This transient band grows in following annealing at 32 K, but then disappears upon annealing above 34 K, suggesting that it may correspond to a reactive intermediate. The band occurs for samples both with and without Au present on the TiO2 surface, but shows a larger intensity in the latter case. Possible assignments for the observed band in light of previous studies from the

  3. Stability assessment of injectable castor oil-based nano-sized emulsion containing cationic droplets stabilized by poloxamer-chitosan emulsifier films. (United States)

    Tamilvanan, S; Kumar, B Ajith; Senthilkumar, S R; Baskar, Raj; Sekharan, T Raja


    The objectives of the present work were to prepare castor oil-based nano-sized emulsion containing cationic droplets stabilized by poloxamer-chitosan emulgator film and to assess the kinetic stability of the prepared cationic emulsion after subjecting it to thermal processing and freeze-thaw cycling. Presence of cryoprotectants (5%, w/w, sucrose +5%, w/w, sorbitol) improved the stability of emulsions to droplet aggregation during freeze-thaw cycling. After storing the emulsion at 4 degrees C, 25 degrees C, and 37 degrees C over a period of up to 6 months, no significant change was noted in mean diameter of the dispersed oil droplets. However, the emulsion stored at the highest temperature did show a progressive decrease in the pH and zeta potential values, whereas the emulsion kept at the lowest temperatures did not. This indicates that at 37 degrees C, free fatty acids were formed from the castor oil, and consequently, the liberated free fatty acids were responsible for the reduction in the emulsion pH and zeta potential values. Thus, the injectable castor oil-based nano-sized emulsion could be useful for incorporating various active pharmaceutical ingredients that are in size from small molecular drugs to large macromolecules such as oligonucleotides.

  4. Cationic triangulenes and helicenes: synthesis, chemical stability, optical properties and extended applications of these unusual dyes. (United States)

    Bosson, Johann; Gouin, Jérôme; Lacour, Jérôme


    Cationic triangulenes and helicenes are highly stable carbocations with planar and helical conformations respectively. These moieties are effective dyes with original absorption and emission properties. Over the last decade, they have received greater attention and are considered as valuable tools for the development of innovative applications. In this review, the synthesis of these unique compounds is presented together with their core chemical and physical properties. Representative applications spanning from surface sciences to biology and chemistry are presented.

  5. DNA association-enhanced physical stability of catanionic vesicles composed of ion pair amphiphile with double-chain cationic surfactant. (United States)

    Lee, Jung; Chang, Chien-Hsiang


    Physical stability control of vesicle/DNA complexes is a key issue for the development of catanionic vesicles composed of ion pair amphiphile (IPA) as DNA carriers. In this work, physical stability characteristics of the complexes of DNA with positively charged catanionic vesicles composed of an IPA and a double-chain cationic surfactant, dihexadecyldimethylammonium bromide (DHDAB), were explored. It was found that in water, the mixed IPA/DHDAB catanionic vesicles became stable when the mole fraction of DHDAB (xDHDAB) was increased up to 0.5. The improved physical stability of the vesicles with a high xDHDAB could be related to the enhanced electrostatic interaction between the vesicles. When the catanionic vesicles interacted with DNA, excellent physical stability was detected for the vesicle/DNA complexes especially with a high xDHDAB. However, this could not be fully explained by the electrostatic interaction effect, and the role of molecular packing within the vesicular bilayers was apparently important. The corresponding Langmuir monolayer study demonstrated that the molecular packing of mixed IPA/DHDAB layers became ordered with DNA association due to inhibited desorption of the positively charged moiety of the IPA. Moreover, the DNA association-induced improvement in the molecular packing of the mixed IPA/DHDAB layers became pronounced with increased xDHDAB. The results imply that one can fabricate catanionic vesicle/DNA complexes with excellent physical stability through the improved molecular packing in the IPA vesicular bilayers with DHDAB addition and DNA association.

  6. Synthesis of cationic hyperbranched multiarm copolymer and its application in self-reducing and stabilizing gold nanoparticles

    Institute of Scientific and Technical Information of China (English)


    A novel hyperbranched multiarm copolymer of HBPO-star-PDEAEMA with a hydrophobic poly(3-ethyl-3-(hydroxymethyl) oxetane)(HBPO) core and many cationic poly(2-(N,N-diethylamino) ethyl methacrylate)(PDEAEMA) arms has been synthesized through an atom transfer radical polymerization(ATRP) method,and been applied to spontaneously reduce and stabilize gold nanoparticles(AuNPs) in water without other additional agents.The size of the nanoparticles could be effectively controlled at about 4 nm,and the nanoparticles are extremely stable in solution without aggregation even for one year.It was found that solution pH and the molar ratio of N/Au have certain effects on the size and stability of AuNPs.This work provides a simple method for the synthesis of uniform and highly stable AuNPs.

  7. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.


    Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

  8. Temperature effects on the stability of gold nanoparticles in the presence of a cationic thermoresponsive copolymer (United States)

    Pamies, Ramón; Zhu, Kaizheng; Kjøniksen, Anna-Lena; Nyström, Bo


    New hybrid complexes composed by a thermoresponsive copolymer and gold nanoparticles (Rh = 22 nm) have been characterized by dynamic light scattering (DLS) and UV-visible spectroscopy. A cationic thermoresponsive triblock copolymer, methoxy-poly(ethylene glycol)- block-poly( N-isopropylacrylamide)- block-poly((3-acrylamidopropyl) trimethyl ammonium chloride), abbreviated as MPEG- b-PNIPAAM- b-PN(+), has been synthesized by atom transfer radical polymerization (ATRP). We have evaluated the thermal response at low concentrations of this triblock copolymer in bulk solution and the effect of concentration on the interaction between this thermosensitive copolymer and the gold nanoparticles (AuNPs) to form new hybrid complexes (60-1000 nm) at different temperatures. The thermosensitive nature of the copolymer causes both aggregation and contraction of the aggregates at elevated temperatures. The AuNPs were found to be separately embedded in the hybrid complexes. Interestingly, the AuNPs prevent macroscopic phase separation of the system at high temperatures.

  9. Enhancement of YBCO thin film thermal stability under 1 ATM oxygen pressure by intermediate Cu2O nanolayer. (United States)

    Cheng, L; Wang, X; Yao, X; Wan, W; Li, F H; Xiong, J; Tao, B W; Jirsa, M


    The melting process of YBa(2)Cu(3)O(x) (YBCO or Y123) films under an oxygen atmosphere was observed in situ by means of high-temperature optical microscopy. The films were classified by pole figure measurement as c-axis oriented, with two different in-plane orientations (denoted as 0 and 45 degrees). In the 45 degrees-oriented films, electron diffraction and high-resolution transmission electron microscopy (HRTEM) detected an intermediate Cu(2)O nanolayer in the vicinity of the interface. The melting mode and the thermal stability of the YBCO thin films with different in-plane orientations were greatly influenced by oxygen partial pressure. Notably, the thermal stability of the 45 degrees-oriented YBCO films dramatically grew with increasing oxygen partial pressure. We attributed this effect to a change in the intermediate Cu(2)O nanolayer thermal stability. We conclude and suggest that the thermal stability of YBCO films can be significantly enhanced by inserting a Cu(2)O buffer nanolayer.

  10. Cross-linked aromatic cationic polymer electrolytes with enhanced stability for high temperature fuel cell applications

    DEFF Research Database (Denmark)

    Ma, Wenjia; Zhao, Chengji; Yang, Jingshuai


    anchoring of the molecule. Combining the excellent thermal stability, the addition of a small amount of diamines enhanced both the chemical and mechanical stability and the phosphoric acid doping (PA) ability of membranes. Fuel cell performance based on impregnated cross-linked membranes have been...... that the diamine-cross-linked membranes using the rigid cross-linker show much improved properties than that using the flexible cross-linker. More properties relating to the feasibility in high temperature proton exchange membrane fuel cell applications were investigated in detail....

  11. Frame Stability of Tunnel‐Structured Cryptomelane Nanofibers: The Role of Tunnel Cations

    DEFF Research Database (Denmark)

    Gao, Tao; Norby, Poul


    The role of tunnel K+ ions on the growth and stability of tunnel‐structured cryptomelane‐type MnO2 nanofibers (denoted as cryptomelane nanofibers hereafter) has been discussed by means of X‐ray diffraction and electron microscopy. Cryptomelane nanofibers with typical diameters of 20–80 nm and len...

  12. A catalytic intermediate and several flavin redox states stabilized by folate-dependent tRNA methyltransferase from Bacillus subtilis. (United States)

    Hamdane, Djemel; Guerineau, Vincent; Un, Sun; Golinelli-Pimpaneau, Beatrice


    The flavoprotein TrmFO catalyzes the C5 methylation of uridine 54 in the TΨC loop of tRNAs using 5,10-methylenetetrahydrofolate (CH(2)THF) as a methylene donor and FAD as a reducing agent. Here, we report biochemical and spectroscopic studies that unravel the remarkable capability of Bacillus subtilis TrmFO to stabilize, in the presence of oxygen, several flavin-reduced forms, including an FADH(•) radical, and a catalytic intermediate endowed with methylating activity. The FADH(•) radical was characterized by high-field electron paramagnetic resonance and electron nuclear double-resonance spectroscopies. Interestingly, the enzyme exhibited tRNA methylation activity in the absence of both an added carbon donor and an external reducing agent, indicating that a reaction intermediate, containing presumably CH(2)THF and FAD hydroquinone, is present in the freshly purified enzyme. Isolation by acid treatment, under anaerobic conditions, of noncovalently bound molecules, followed by mass spectrometry analysis, confirmed the presence in TrmFO of nonmodified FAD. Addition of formaldehyde to the purified enzyme protects the reduced flavins from decay by probably preventing degradation of CH(2)THF. The absence of air-stable reduced FAD species during anaerobic titration of oxidized TrmFO, performed in the absence or presence of added CH(2)THF, argues against their thermodynamic stabilization but rather implicates their kinetic trapping by the enzyme. Altogether, the unexpected isolation of a stable catalytic intermediate suggests that the flavin-binding pocket of TrmFO is a highly insulated environment, diverting the reduced FAD present in this intermediate from uncoupled reactions.

  13. Comparing the short and long term stability of biodegradable, ceramic and cation exchange membranes in microbial fuel cells. (United States)

    Winfield, Jonathan; Chambers, Lily D; Rossiter, Jonathan; Ieropoulos, Ioannis


    The long and short-term stability of two porous dependent ion exchange materials; starch-based compostable bags (BioBag) and ceramic, were compared to commercially available cation exchange membrane (CEM) in microbial fuel cells. Using bi-directional polarisation methods, CEM exhibited power overshoot during the forward sweep followed by significant power decline over the reverse sweep (38%). The porous membranes displayed no power overshoot with comparably smaller drops in power during the reverse sweep (ceramic 8%, BioBag 5.5%). The total internal resistance at maximum power increased by 64% for CEM compared to 4% (ceramic) and 6% (BioBag). Under fixed external resistive loads, CEM exhibited steeper pH reductions than the porous membranes. Despite its limited lifetime, the BioBag proved an efficient material for a stable microbial environment until failing after 8 months, due to natural degradation. These findings highlight porous separators as ideal candidates for advancing MFC technology in terms of cost and operation stability.

  14. RgBF2(+) complexes (Rg = Ar, Kr, and Xe): the cations with large stabilities. (United States)

    Lv, Zhi; Chen, Guang-Hui; Li, Dan; Wu, Di; Huang, Xiao-Chun; Li, Zhi-Ru; Liu, Wen-Guang


    Rare gas containing cations with general formula [Rg, B, 2F](+) have been investigated theoretically by second-order Mo̸ller-Plesset perturbation, coupled cluster, and complete active space self-consistent field levels of theory with correlation-consistent basis sets. Totally two types of minima, i.e., boron centered C(2) (v) symmetried RgBF(2) (+) (Rg = Ar, Kr, and Xe) which can be viewed as loss of F(-) from FRgBF(2) and linear FRgBF(+) (Rg = Kr and Xe) are obtained at the CCSD(T)∕aug-cc-pVTZ∕SDD and CASSCF(10,8)∕aug-cc-pVTZ∕SDD levels, respectively. It is shown that the RgBF(2) (+) are global minima followed by FRgBF(+) at 170.9 and 142.2 kcal∕mol on the singlet potential-energy surfaces of [Rg, B, 2F](+) (Rg = Kr and Xe) at the CASPT2(10,8) ∕aug-cc-pVTZ∕SDD∕∕CASSCF(10,8)∕aug-cc-pVTZ∕SDD, respectively. The interconversion barrier heights between RgBF(2) (+) and FRgBF(+) (Rg = Kr and Xe) are at least 39 kcal∕mol. In addition, no dissociation transition state associated with RgBF(2) (+) and FRgBF(+) can be found. This suggests that RgBF(2) (+) (Rg = Ar, Kr, and Xe) can exist as both thermodynamically and kinetically stable species, while linear FRgBF(+) (Rg = Kr and Xe) can exist as metastable species compared with the lowest dissociation limit energies just like isoelectronic linear FRgBO and FRgBN(-). From natural bond orbital and atoms-in-molecules calculations, it is found that the positive charge is mainly located on Rg and boron atoms for both types of minima, the Rg-B bonds of ArBF(2) (+), KrBF(2) (+), and XeBF(2) (+) are mostly electrostatic, thus can be viewed as ion-induced dipole interaction; while that of linear FKrBF(+) and FXeBF(+) are covalent in nature. The previous experimental observation of ArBF(2) (+) by Pepi et al. [J. Phys. Chem. B. 110, 4492 (2006)] should correspond to C(2) (v) minimum. The presently predicted spectroscopies of KrBF(2) (+), XeBF(2) (+), FKrBF(+), and FXeBF(+) should be helpful for their experimental

  15. High stability of electro-transport and magnetism against the A-site cation disorder in SrRuO3 (United States)

    Wang, Y. L.; Liu, M. F.; Liu, R.; Xie, Y. L.; Li, X.; Yan, Z. B.; Liu, J.-M.


    It is known that the electro-transport and magnetism of perovskite alkaline-earth ruthenate oxides are sensitive to the lattice distortion associated with the A-site cation size. Orthorhombic CaRuO3 and cubic BaRuO3 exhibit distinctly different electro-transport and magnetic properties from orthorhombic SrRuO3. It has been suggested that SrRuO3 can be robust against some intrinsic/external perturbations but fragile against some others in terms of electro-transport and magnetism, and it is our motivation to explore such stability against the local site cation disorder. In this work, we prepare a set of SrRuO3-based samples with identical averaged A-site size but different A-site cation disorder (size mismatch) by Ca and Ba co-substitution of Sr. It is revealed that the electro-transport and magnetism of SrRuO3 demonstrate relatively high stability against this A-site cation disorder, characterized by the relatively invariable electrical and magnetic properties in comparison with those of SrRuO3 itself. A simple electro-transport network model is proposed to explain quantitatively the measured behaviors. The present work suggests that SrRuO3 as an itinerant electron ferromagnetic metal possesses relatively high robustness against local lattice distortion and cation occupation disorder.

  16. High stability of electro-transport and magnetism against the A-site cation disorder in SrRuO3. (United States)

    Wang, Y L; Liu, M F; Liu, R; Xie, Y L; Li, X; Yan, Z B; Liu, J-M


    It is known that the electro-transport and magnetism of perovskite alkaline-earth ruthenate oxides are sensitive to the lattice distortion associated with the A-site cation size. Orthorhombic CaRuO3 and cubic BaRuO3 exhibit distinctly different electro-transport and magnetic properties from orthorhombic SrRuO3. It has been suggested that SrRuO3 can be robust against some intrinsic/external perturbations but fragile against some others in terms of electro-transport and magnetism, and it is our motivation to explore such stability against the local site cation disorder. In this work, we prepare a set of SrRuO3-based samples with identical averaged A-site size but different A-site cation disorder (size mismatch) by Ca and Ba co-substitution of Sr. It is revealed that the electro-transport and magnetism of SrRuO3 demonstrate relatively high stability against this A-site cation disorder, characterized by the relatively invariable electrical and magnetic properties in comparison with those of SrRuO3 itself. A simple electro-transport network model is proposed to explain quantitatively the measured behaviors. The present work suggests that SrRuO3 as an itinerant electron ferromagnetic metal possesses relatively high robustness against local lattice distortion and cation occupation disorder.

  17. Relative Stability of the Key Enamine,Oxazolidinone, and Imine Intermediates in Some Proline-catalyzed Asymmetric Reactions

    Institute of Scientific and Technical Information of China (English)

    HU Yi-Fan; LU Xin


    Many proline-catalyzed asymmetric addition reactions with ketones as substrates were assumed to involve a key intermediate, an enamine, produced by the condensation of proline and ketone. In this paper, the key intermediate enamines derived from L-proline and cyclohexanone (or acetone) as well as the corresponding oxazolidinone and imine tautomers have been investigated by means of density functional calculations at the B3LYP/6-311+G** level. The predicted order of stability for these tautomers is oxazolidinones > enamines > imines in gas phase and oxazolidinones > imines > enamines in aprotic THF solvent. This prediction explains why enamine intermediate can not be observed experimentally. The predicted energy/enthalpy difference between the formal oxazolidinone structure and the zwitterionic imine structures is very small in THF solvent, suggesting the oxazolidinone-to-imine tautomerization can be readily induced in solvent. 13C NMR chemical shifts of the oxazolidinone and imine structures have been computed and used to explain the experimental NMR spectra observed in oxazolidinone-to-imine tautomerization induced by protic solvent.

  18. Haemostatic role of intermediate filaments in adhered platelets: importance of the membranous system stability. (United States)

    Cerecedo, Doris; Martínez-Vieyra, Ivette; Mondragón, Ricardo; Mondragón, Mónica; González, Sirenia; Galván, Iván J


    The role of platelets in coagulation and the haemostatic process was initially suggested two centuries ago, and under appropriate physiological stimuli, these undergo abrupt morphological changes, attaching and spreading on damaged endothelium, preventing bleeding. During the adhesion process, platelet cytoskeleton reorganizes generating compartments in which actin filaments, microtubules, and associated proteins are arranged in characteristic patterns mediating crucial events, such as centralization of their organelles, secretion of granule contents, aggregation with one another to form a haemostatic plug, and retraction of these aggregates. However, the role of Intermediate filaments during the platelet adhesion process has not been explored. J. Cell. Biochem. 114: 2050-2060, 2013. © 2013 Wiley Periodicals, Inc.

  19. Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials. (United States)

    Neukirch, Amanda J; Nie, Wanyi; Blancon, Jean-Christophe; Appavoo, Kannatassen; Tsai, Hsinhan; Sfeir, Matthew Y; Katan, Claudine; Pedesseau, Laurent; Even, Jacky; Crochet, Jared J; Gupta, Gautam; Mohite, Aditya D; Tretiak, Sergei


    Solution-processed organometallic perovskites have rapidly developed into a top candidate for the active layer of photovoltaic devices. Despite the remarkable progress associated with perovskite materials, many questions about the fundamental photophysical processes taking place in these devices, remain open. High on the list of unexplained phenomena are very modest mobilities despite low charge carrier effective masses. Moreover, experiments elucidate unique degradation of photocurrent affecting stable operation of perovskite solar cells. These puzzles suggest that, while ionic hybrid perovskite devices may have efficiencies on par with conventional Si and GaAs devices, they exhibit more complicated charge transport phenomena. Here we report the results from an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies using both periodic boundary conditions and isolated structures. Using the hybrid density functional theory, we found that volumetric strain in a CsPbI3 cluster creates a polaron with binding energy of around 300 and 900 meV for holes and electrons, respectively. In the MAPbI3 (MA = CH3NH3) cluster, both volumetric strain and MA reorientation effects lead to larger binding energies at around 600 and 1300 meV for holes and electrons, respectively. Such large reorganization energies suggest appearance of small polarons in organometallic perovskite materials. The fact that both volumetric lattice strain and MA molecular rotational degrees of freedom can cooperate to create and stabilize polarons indicates that in order to mitigate this problem, formamidinium (FA = HC(NH2)2) and cesium (Cs) based crystals and alloys, are potentially better materials for solar cell and other optoelectronic applications.

  20. Development of helix-stabilized cell-penetrating peptides containing cationic α,α-disubstituted amino acids as helical promoters. (United States)

    Yamashita, Hiroko; Misawa, Takashi; Oba, Makoto; Tanaka, Masakazu; Naito, Mikihiko; Kurihara, Masaaki; Demizu, Yosuke


    Cell-penetrating peptides (CPP) have attracted many scientists' attention as intracellular delivery tools due to their high cargo molecule transportation efficiency and low cytotoxicity. Therefore, in many research fields CPP, such as HIV-Tat and oligoarginine (Rn), are used to deliver hydrophilic drugs and biomolecules, including proteins, DNA, and RNA. We designed four types of CPP that contained cationic α,α-disubstituted amino acids (Api(C2Gu) and Api(C4Gu)) as helical promoters; i.e., 1-4 [FAM-β-Ala-(l-Arg-l-Arg-Xaa)3-(Gly)3-NH2 (1: Xaa=Api(C2Gu), 2: Xaa=Api(C4Gu)), 3: FAM-β-Ala-(l-Arg)8-Api(C2Gu)-(Gly)3-NH2, and 4: FAM-β-Ala-(l-Arg)5-Api(C2Gu)-(l-Arg)2-Api(C2Gu)-(Gly)3-NH2], and investigated their preferred secondary structures and cell membrane-penetrating ability. As a result, we found that the permeation efficiency of the CPP was affected by the number of helical promoters in their sequences. Specially, peptide 1, which contained three Api(C2Gu) residues, formed a stable helical structure and passed through the cell membrane more efficiently than the other peptides. Moreover, it was demonstrated that the spatial arrangement of the peptides' side chains also influenced their permeability and the helical stabilization of their main chains.

  1. Do Cation-π Interactions Exist in Bacteriorhodopsin

    Institute of Scientific and Technical Information of China (English)

    HU Kun-Sheng; WANG Guang-Yu; HE Jin-An


    Metal ions are essential to the structure and physiological functions of bacteriorhodopsin. Experimental evidence suggests the existence of specific cation binding to the negatively charged groups of Asp85 and Asp212 via an electrostatic interaction. However, only using electrostatic force is not enough to explain the role of the metal cations because the carboxylate of Asp85 is well known to be protonated in the M intermediate. Considering the presence of some aromatic amino acid residues in the vicinity of the retinal pocket, the existence of cation-π interactions between the metal cation and aromatic amino acid residues is suggested. Obviously, introduction of this kind of interaction is conducive to understanding the effects of the metal cations and aromatic amino acid residues inside the protein on the structural stability and proton pumping of bacteriorhodopsin.

  2. Radiation stability of cations in ionic liquids. 5. Task-specific ionic liquids consisting of biocompatible cations and the puzzle of radiation hypersensitivity. (United States)

    Shkrob, Ilya A; Marin, Timothy W; Wishart, James F; Grills, David C


    In 1953, an accidental discovery by Melvin Calvin and co-workers provided the first example of a solid (the α-polymorph of choline chloride) showing hypersensitivity to ionizing radiation: under certain conditions, the radiolytic yield of decomposition approached 5 × 10(4) per 100 eV (which is 4 orders of magnitude greater than usual values), suggesting an uncommonly efficient radiation-induced chain reaction. Twenty years later, the still-accepted mechanism for this rare condition was suggested by Martyn Symons, but no validation for this mechanism has been supplied. Meanwhile, ionic liquids and deep eutectic mixtures that are based on choline, betainium, and other derivitized natural amino compounds are presently finding an increasing number of applications as diluents in nuclear separations, where the constituent ions are exposed to ionizing radiation that is emitted by decaying radionuclides. Thus, the systems that are compositionally similar to radiation hypersensitive solids are being considered for use in high radiation fields, where this property is particularly undesirable! In Part 5 of this series on organic cations, we revisit the phenomenon of radiation hypersensitivity and explore mechanistic aspects of radiation-induced reactions involving this class of task-specific, biocompatible, functionalized cations, both in ionic liquids and in reference crystalline compounds. We demonstrate that Symons' mechanism needs certain revisions and rethinking, and suggest its modification. Our reconsideration suggests that there cannot be conditions leading to hypersensitivity in ionic liquids.

  3. A threonine stabilizes the NiC and NiR catalytic intermediates of [NiFe]-hydrogenase. (United States)

    Abou-Hamdan, Abbas; Ceccaldi, Pierre; Lebrette, Hugo; Gutiérrez-Sanz, Oscar; Richaud, Pierre; Cournac, Laurent; Guigliarelli, Bruno; De Lacey, Antonio L; Léger, Christophe; Volbeda, Anne; Burlat, Bénédicte; Dementin, Sébastien


    The heterodimeric [NiFe] hydrogenase from Desulfovibrio fructosovorans catalyzes the reversible oxidation of H2 into protons and electrons. The catalytic intermediates have been attributed to forms of the active site (NiSI, NiR, and NiC) detected using spectroscopic methods under potentiometric but non-catalytic conditions. Here, we produced variants by replacing the conserved Thr-18 residue in the small subunit with Ser, Val, Gln, Gly, or Asp, and we analyzed the effects of these mutations on the kinetic (H2 oxidation, H2 production, and H/D exchange), spectroscopic (IR, EPR), and structural properties of the enzyme. The mutations disrupt the H-bond network in the crystals and have a strong effect on H2 oxidation and H2 production turnover rates. However, the absence of correlation between activity and rate of H/D exchange in the series of variants suggests that the alcoholic group of Thr-18 is not necessarily a proton relay. Instead, the correlation between H2 oxidation and production activity and the detection of the NiC species in reduced samples confirms that NiC is a catalytic intermediate and suggests that Thr-18 is important to stabilize the local protein structure of the active site ensuring fast NiSI-NiC-NiR interconversions during H2 oxidation/production.

  4. Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives – their stability, complexation ability in solution or when deposited on solid anionic surface


    Martin Popr; Filippov, Sergey K; Nikolai Matushkin; Juraj Dian; Jindřich Jindřich


    The thermal stability of the monosubstituted cationic cyclodextrin (CD) derivatives PEMEDA-β-CD and PEMPDA-β-CD, which differ in their substituent linker length (ethylene and propylene, respectively), was studied via 1H NMR experiments. PEMPDA-β-CD exhibited higher resistance towards the Hofmann degradation and was chosen as a more suitable host molecule for further studies. Inclusion properties of PEMPDA-β-CD in solution with a series of simple aromatic guests (salicylic acid, p-methoxypheno...

  5. Atomistic structural ensemble refinement reveals non-native structure stabilizes a sub-millisecond folding intermediate of CheY (United States)

    Shi, Jade; Nobrega, R. Paul; Schwantes, Christian; Kathuria, Sagar V.; Bilsel, Osman; Matthews, C. Robert; Lane, T. J.; Pande, Vijay S.


    The dynamics of globular proteins can be described in terms of transitions between a folded native state and less-populated intermediates, or excited states, which can play critical roles in both protein folding and function. Excited states are by definition transient species, and therefore are difficult to characterize using current experimental techniques. Here, we report an atomistic model of the excited state ensemble of a stabilized mutant of an extensively studied flavodoxin fold protein CheY. We employed a hybrid simulation and experimental approach in which an aggregate 42 milliseconds of all-atom molecular dynamics were used as an informative prior for the structure of the excited state ensemble. This prior was then refined against small-angle X-ray scattering (SAXS) data employing an established method (EROS). The most striking feature of the resulting excited state ensemble was an unstructured N-terminus stabilized by non-native contacts in a conformation that is topologically simpler than the native state. Using these results, we then predict incisive single molecule FRET experiments as a means of model validation. This study demonstrates the paradigm of uniting simulation and experiment in a statistical model to study the structure of protein excited states and rationally design validating experiments. PMID:28272524

  6. Storage stability of a commercial hen egg yolk powder in dry and intermediate-moisture food matrices. (United States)

    Rao, Qinchun; Fisher, Mary Catherine; Guo, Mufan; Labuza, Theodore P


    Quality loss in intermediate-moisture foods (IMF) such as high-protein nutrition bars (HPNB) in the form of hardening, nonenzymatic browning, and free amino group loss is a general concern for the manufacturers. To measure the extent of quality loss over time in terms of these negative attributes, through changing the ratio by weight between two commercial spray-dried hen egg powders, egg white (DEW) and egg yolk (DEY), the storage stability of 10 IMF systems (water activity (aw) ∼ 0.6) containing 5% glycerol, 10% shortening, 35% protein, and 50% sweetener (either maltitol or 50% high-fructose corn syrup/50% corn syrup (HFCS/CS)) were studied. Additionally, the storage stability of the DEY powder itself was investigated. Overall, during storage at different temperatures (23, 35, and 45 °C), the storage stability of DEY in dry and IMF matrices was mainly controlled by the coaction of three chemical reactions (disulfide bond interaction, Maillard reaction, and lipid oxidation). The results showed that by replacing 25% of DEW in an IMF model system with DEY, the rate of bar hardening was significantly lower than that of the models with only DEW at all temperatures due to the softening effect of the fat in DEY. Furthermore, the use of maltitol instead of HFCS/CS in all bar systems not only resulted in decreased hardness but also drastically decreased the change in the total color difference (ΔE*). Interestingly, there was no significant loss of free amino groups in the maltitol systems at any DEW/DEY ratio.

  7. Engineering of CH3 NH3 PbI3 Perovskite Crystals by Alloying Large Organic Cations for Enhanced Thermal Stability and Transport Properties. (United States)

    Peng, Wei; Miao, Xiaohe; Adinolfi, Valerio; Alarousu, Erkki; El Tall, Omar; Emwas, Abdul-Hamid; Zhao, Chao; Walters, Grant; Liu, Jiakai; Ouellette, Olivier; Pan, Jun; Murali, Banavoth; Sargent, Edward H; Mohammed, Omar F; Bakr, Osman M


    The number of studies on organic-inorganic hybrid perovskites has soared in recent years. However, the majority of hybrid perovskites under investigation are based on a limited number of organic cations of suitable sizes, such as methylammonium and formamidinium. These small cations easily fit into the perovskite's three-dimensional (3D) lead halide framework to produce semiconductors with excellent charge transport properties. Until now, larger cations, such as ethylammonium, have been found to form 2D crystals with lead halide. Here we show for the first time that ethylammonium can in fact be incorporated coordinately with methylammonium in the lattice of a 3D perovskite thanks to a balance of opposite lattice distortion strains. This inclusion results in higher crystal symmetry, improved material stability, and markedly enhanced charge carrier lifetime. This crystal engineering strategy of balancing opposite lattice distortion effects vastly increases the number of potential choices of organic cations for 3D perovskites, opening up new degrees of freedom to tailor their optoelectronic and environmental properties.

  8. On the Electronic Spectroscopy of Closed Shell Cations Derived from Resonance Stabilized Radicals: Insights from Theory and Franck-Condon Analysis (United States)

    Troy, Tyler P.; Kable, Scott H.; Schmidt, Timothy W.; Reid, Scott A.


    Recent attention has been directed on closed shell aromatic cations as potential carriers of the diffuse interstellar bands. The spectra of mass-selected, matrix-isolated benzylium and tropylium cations were recently reported [Nagy, A., Fulara, J., Garkusha, I. and Maier, J. P. (2011), Angew. Chem. Int. Ed., 50: 3022-3025]. The benzylium spectrum shows an extended progression in a low frequency (510 cm-1) ring distortion mode. Modeling of the benzylium spectrum using (TD)DFT and MCSCF-PT2 methods in concert with multidimensional Franck-Condon (FC) analysis is found to yield excellent agreement with the experimental spectrum. We extended this analysis to larger (2 and 3 ring) PAH cations derived from resonance stabilized radicals, which are predicted to show strong S0 → Sn transitions in the visible region. The FC progression is significantly quenched in the larger species, and our results for 1-napthylmethylium are in excellent agreement with very recent experiments [Nagy, A., Fulara, J., and Maier, J. P. (2011), J. Am. Chem. Soc., 133, 19796]. Since carriers of the DIBs should exhibit spectra dominated by a single vibronic transition, our results demonstrate that closed-shell cations may present spectra with the required properties. Furthermore, the calculated ionization energies of a range of CSCs were found to be in the 13-14 eV range, consistent with variations in behaviour of the DIB carriers with respect to various astrophysical environments.

  9. Reactions of acetone oxide stabilized Criegee intermediate with SO2, NO2, H2O and O3 (United States)

    Kukui, Alexandre; Chen, Hui; Xiao, Shan; Mellouki, Wahid; Daële, Veronique


    Atmospheric aerosol particles represent a critical component of the atmosphere, impacting global climate, regional air pollution, and human health. The formation of new atmospheric particles and their subsequent growth to larger sizes are the key processes for understanding of the aerosol effects. Sulphuric acid, H2SO4, has been identified to play the major role in formation of new atmospheric particles and in subsequent particle growth. Until recently the reaction of OH with SO2 has been considered as the only important source of H2SO4 in the atmosphere. However, recently it has been suggested that the oxidation of SO2 by Criegee biradicals can be a significant additional atmospheric source of H2SO4 comparable with the reaction of SO2 with OH. Here we present some results about the reactions of the acetone oxide stabilized Criegee intermediate, (CH3)2=OO, produced in the reaction of 2,3-dimethyl-butene (TME) with O3. The formation of the H2SO4 in the reaction of acetone oxide with SO2 was investigated in the specially constructed atmospheric pressure laminar flow reactor. The Criegee intermediate was generated by ozonolysis of TME. The H2SO4, generated by addition of SO2, was directly monitored with Chemical Ionization Mass Spectrometer (SAMU, LPC2E). Relative rates of reactions of acetone oxide with SO2, NO2, H2O and ozone were determined from the dependencies of the H2SO4 yield at different concentrations of the reactants. Atmospheric applications of the obtained results are discussed in relation to the importance of this additional H2SO4 formation pathway compared to the reaction of OH with SO2.

  10. Unfolding and aggregation of monoclonal antibodies on cation exchange columns: effects of resin type, load buffer, and protein stability. (United States)

    Guo, Jing; Carta, Giorgio


    The chromatographic behavior of a monoclonal antibody (mAb) that exhibits a pronounced two-peak elution behavior is studied for a range of strong cation exchange resins and with varying load buffer pH and composition. Six stationary phases are considered, including two tentacle-type resins (Fractogel EMD SO3-(M) and Eshmuno S), a resin with grafted polymeric surface extenders (Nuvia S), a resin with a bimodal pore size distribution (POROS HS 50), and two macroporous resins without polymer grafts (Source 30S and UNOsphere Rapid S). The two-peak elution behavior is very pronounced for the tentacle and polymer-grafted resins and for POROS HS 50, but is essentially absent for the two macroporous resins. The extent of this behavior decreases as the buffer pH and concentration increase and, consequently, mAb binding becomes weaker. Replacing sodium with arginine as the buffer counterion, which is expected to decrease the mAb binding strength, nearly completely eliminates the two-peak behavior, while replacing sodium with tetra-n-butylammonium hydroxide, which is expected to increase the mAb binding strength, dramatically exacerbate the effect. As shown by hydrogen-deuterium exchange mass spectrometry (HX-MS), the two-peak elution behavior is related to conformational changes that occur when the mAb binds. These changes result in increased solvent exposure of specific peptides in the Fc-region for either the Fractogel or the Nuvia resin. No significant conformational changes were seen by HX-MS when the mAb was bound to the UNOsphere resin or on the Fractogel resin when arginine was used in lieu of sodium as the load buffer counterion. Experiments with two additional mAbs on the Fractogel resin show that the two-peak elution behavior is dependent on the particular antibody. Circular dichroism suggests that the propensity of different mAbs to either precipitate directly or to form stabilizing intermolecular structures upon exposure to thermal stress can be related to their

  11. Hydration, Ionic Valence and Cross-Linking Propensities of Cations Determine the Stability of Lipopolysaccharide (LPS) Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Nascimento, Agrinaldo; Pontes, Frederico J.; Lins, Roberto D.; Soares, Thereza A.


    The supra-molecular structure of LPS aggregates governs outer membrane permeability and activation of the host immune response during Gram-negative bacterial infections. Molecular dynamics simulations unveil at atomic resolution 10 the subtle balance between cation hydration and cross-link ability in modulating phase transitions of LPS membranes.

  12. Acid decomposition and thiourea leaching of silver from hazardous jarosite residues: Effect of some cations on the stability of the thiourea system. (United States)

    Calla-Choque, D; Nava-Alonso, F; Fuentes-Aceituno, J C


    The recovery of silver from hazardous jarosite residues was studied employing thiourea as leaching agent at acid pH and 90°C. The stability of the thiourea in synthetic solutions was evaluated in the presence of some cations that can be present in this leaching system: cupric and ferric ions as oxidant species, and zinc, lead and iron as divalent ions. Two silver leaching methods were studied: the simultaneous jarosite decomposition-silver leaching, and the jarosite decomposition followed by the silver leaching. The study with synthetic solutions demonstrated that cupric and ferric ions have a negative effect on thiourea stability due to their oxidant properties. The effect of cupric ions is more significant than the effect of ferric ions; other studied cations (Fe(2+), Zn(2+), Pb(2+)) had no effect on the stability of thiourea. When the decomposition of jarosite and the silver leaching are carried out simultaneously, 70% of the silver can be recovered. When the acid decomposition was performed at pH 0.5 followed by the leaching step at pH 1, total silver recovery increased up to 90%. The zinc is completely dissolved with any of these processes while the lead is practically insoluble with these systems producing a lead-rich residue.

  13. Novel Behavior of Thiiranium Radical Cation Intermediates. Reactions of Dimethyl Disulfide with Alkenes in the Presence of Pd(OAc2

    Directory of Open Access Journals (Sweden)

    Shingo Iizuka


    Full Text Available Reaction of dimethyl disulfide (1 with cyclohexene (2a in AcOH in the presence of Pd(OAc2 yields trans-1-acetoxy-2-methylcyclohexane (3a. The equivalent reactions with hex-1-ene (2b and 2-methylpent-1-ene (2c or 1-methylcyclohex-1-ene (2d preferentially give anti-Markovnikov and Markovnikov adducts 4 and 3, respectively, by acetoxymethylthiolation of the alkene. The Markovnikov regioselectivity 3b/4b for the reaction with 2b is higher than that for the reaction using AgOAc instead of Pd(OAc2, which proceeds via a thiiranium ion. Addition of a polar solvent (MeCN or MeNO2 to the reactions with 2b or 2c using Pd(OAc2 abnormally decreases the Markovnikov regioselectivity. The total yield of 3 and 4 increases with an increased concentration of AcOH. Compounds 3 and 4 are also formed and the reactions in MeCN or MeNO2 not containing AcOH. A solution of Pd(OAc2 in 1 exhibits λmax 380 nm (log ε 3.6 assigned to the absorption of a relatively stable sulfonium salt. These indicate that the reactions using Pd(OAc2 proceed by SN2 ringopening of a new type of thiiranium radical cations paired with −OAc via the sulfonium salts. The insensitivity of the 3/4 ratios to the reaction time at 25-60°C in the reactions with 2c-d shows the ring-opening to be controlled kinetically, but the increased ratio with reaction time at 116°C in the reaction with 2b suggests that the ring-opening is thermodynamically governed. The reaction product with 2d also undergoes a skeletal rearrangement to a thietanium radical cation to give 1-acetoxymethyl-2-methylthiocyclohexane.

  14. Intermediates in monensin biosynthesis: A late step in biosynthesis of the polyether ionophore monensin is crucial for the integrity of cation binding (United States)

    Spencer, Jonathan B; Leadlay, Peter F


    Summary Polyether antibiotics such as monensin are biosynthesised via a cascade of directed ring expansions operating on a putative polyepoxide precursor. The resulting structures containing fused cyclic ethers and a lipophilic backbone can form strong ionophoric complexes with certain metal cations. In this work, we demonstrate for monensin biosynthesis that, as well as ether formation, a late-stage hydroxylation step is crucial for the correct formation of the sodium monensin complex. We have investigated the last two steps in monensin biosynthesis, namely hydroxylation catalysed by the P450 monooxygenase MonD and O-methylation catalysed by the methyl-transferase MonE. The corresponding genes were deleted in-frame in a monensin-overproducing strain of Streptomyces cinnamonensis. The mutants produced the expected monensin derivatives in excellent yields (ΔmonD: 1.13 g L−1 dehydroxymonensin; ΔmonE: 0.50 g L−1 demethylmonensin; and double mutant ΔmonDΔmonE: 0.34 g L−1 dehydroxydemethylmonensin). Single crystals were obtained from purified fractions of dehydroxymonensin and demethylmonensin. X-ray structure analysis revealed that the conformation of sodium dimethylmonensin is very similar to that of sodium monensin. In contrast, the coordination of the sodium ion is significantly different in the sodium dehydroxymonensin complex. This shows that the final constitution of the sodium monensin complex requires this tailoring step as well as polyether formation. PMID:24605157

  15. Intermediates in monensin biosynthesis: A late step in biosynthesis of the polyether ionophore monensin is crucial for the integrity of cation binding

    Directory of Open Access Journals (Sweden)

    Wolfgang Hüttel


    Full Text Available Polyether antibiotics such as monensin are biosynthesised via a cascade of directed ring expansions operating on a putative polyepoxide precursor. The resulting structures containing fused cyclic ethers and a lipophilic backbone can form strong ionophoric complexes with certain metal cations. In this work, we demonstrate for monensin biosynthesis that, as well as ether formation, a late-stage hydroxylation step is crucial for the correct formation of the sodium monensin complex. We have investigated the last two steps in monensin biosynthesis, namely hydroxylation catalysed by the P450 monooxygenase MonD and O-methylation catalysed by the methyl-transferase MonE. The corresponding genes were deleted in-frame in a monensin-overproducing strain of Streptomyces cinnamonensis. The mutants produced the expected monensin derivatives in excellent yields (ΔmonD: 1.13 g L−1 dehydroxymonensin; ΔmonE: 0.50 g L−1 demethylmonensin; and double mutant ΔmonDΔmonE: 0.34 g L−1 dehydroxydemethylmonensin. Single crystals were obtained from purified fractions of dehydroxymonensin and demethylmonensin. X-ray structure analysis revealed that the conformation of sodium dimethylmonensin is very similar to that of sodium monensin. In contrast, the coordination of the sodium ion is significantly different in the sodium dehydroxymonensin complex. This shows that the final constitution of the sodium monensin complex requires this tailoring step as well as polyether formation.

  16. Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives – their stability, complexation ability in solution or when deposited on solid anionic surface

    Directory of Open Access Journals (Sweden)

    Martin Popr


    Full Text Available The thermal stability of the monosubstituted cationic cyclodextrin (CD derivatives PEMEDA-β-CD and PEMPDA-β-CD, which differ in their substituent linker length (ethylene and propylene, respectively, was studied via 1H NMR experiments. PEMPDA-β-CD exhibited higher resistance towards the Hofmann degradation and was chosen as a more suitable host molecule for further studies. Inclusion properties of PEMPDA-β-CD in solution with a series of simple aromatic guests (salicylic acid, p-methoxyphenol and p-nitroaniline were determined by isothermal titration calorimetry (ITC and compared to the native β-CD. Permanently charged cationic CD derivatives were successfully deposited on the anionic solid surface of polymeric Nafion® 117 membrane via electrostatic interactions. Deposition kinetics and coverage of the surface were determined by ELSD. Finally, the ability of the CD derivatives bound to the solid surface to encapsulate aromatic compounds from aqueous solution was measured by UV–vis spectroscopy. The obtained results are promising for future industrial applications of the monosubstituted β-CD derivatives, because the preparation of cationic CD derivatives is applicable in large scale, without the need of chromatographic purification. Their ionic deposition on a solid surface is simple, yet robust and a straightforward process as well.

  17. Raman studies of cation distribution and thermal stability of epitaxial spinel NiCo2O4 films (United States)

    Iliev, M. N.; Silwal, P.; Loukya, B.; Datta, R.; Kim, D. H.; Todorov, N. D.; Pachauri, N.; Gupta, A.


    Epitaxial thin films of spinel NiCo2O4 (NCO) grown on MgAl2O4 (001) substrates are reported to exhibit dramatic changes in the magnetic and transport properties with deposition temperature. While films grown at lower temperatures (<450°C) are ferrimagnetic with metallic characteristics, those grown at higher temperatures are non-magnetic and insulating. Detailed polarized Raman spectroscopy studies indicate that the higher temperature films have close to the ideal inverse spinel cation distribution, Co3+[Ni2+Co3+]O42-, whereas those deposited at lower temperature are characterized by mixed cation/charge distribution at both the tetragonal (A) and octahedral (B) sites. Additionally, temperature-dependent Raman studies demonstrate that, unlike bulk polycrystalline samples, all the NCO films are robust against thermal treatment with full reversibility after annealing at 600°C in oxygen and air. However, partial decomposition is observed after annealing in vacuum.

  18. Review of the thermal stability and cation exchange properties of the zeolite minerals clinoptilolite, mordenite, and analcime; applications to radioactive waste isolation in silicic tuff

    Energy Technology Data Exchange (ETDEWEB)

    Smyth, J.R.; Caporuscio, F.A.


    Silicic tuffs of the southern Great Basin and basalts of the Columbia River Plateau are under investigation as potential host rocks for high- and intermediate-level radioactive wastes. Nonwelded and partially welded tuffs may contain major amounts (> 50%) of the zeolite minerals clinoptilolite, mordenite, and analcime. Densely welded tuffs and some basalt flows may contain clinoptilolite as fracture filling that limits the permeability of these rocks. The cation exchange properties of these zeolite minerals allow them to pose a formidable natural barrier to the migration of cationic species of various radionuclides in aqueous solutions. However, these minerals are unstable at elevated temperatures and at low water-vapor pressures and may break down either by reversible dehydration or by irreversible mineralogical reactions. All the breakdown reactions occurring at increased temperature involve a net volume reduction and evolution of fluids. Thus, they may provide a pathway (shrinkage fractures) and a driving force (fluid pressure) for release of radionuclides to the biosphere. These reactions may be avoided by keeping zeolite-bearing horizons saturated with water and below about 85{sup 0}C. This may restrict allowable gross thermal loadings in waste repositories in volcanic rocks.

  19. Intergroup biases of the intermediate-status group: the effect of stability and instability of social stratification. (United States)

    Caricati, Luca; Monacelli, Nadia


    In two studies, the effect of instability of social stratification on intergroup behaviour of the intermediate-status group was investigated. In both studies, participants were categorised in the intermediate-status group. In Study 1, perceived instability was measured. Results show that the more social stratification was perceived as stable, the more intermediate-status group members were biased against the high-status group. Biases against both high- and low-status groups tended to become similar as social stratification was perceived as more unstable. In Study 2, instability was manipulated in upward and downward conditions. Results showed that, in the upwardly unstable condition, intermediate-status group members were more biased against high-status group, while in the downwardly unstable condition they were more biased against the low-status group.

  20. Structure and stability of hexa-aqua V(III) cations in vanadium redox flow battery electrolytes. (United States)

    Vijayakumar, M; Li, Liyu; Nie, Zimin; Yang, Zhenguo; Hu, JianZhi


    The vanadium(III) cation structure in mixed acid based electrolyte solution from vanadium redox flow batteries is studied by (17)O and (35/37)Cl nuclear magnetic resonance (NMR) spectroscopy, electronic spectroscopy and density functional theory (DFT) based computational modelling. Both computational and experimental results reveal that the V(III) species can complex with counter anions (sulfate/chlorine) depending on the composition of its solvation sphere. By analyzing the powder precipitate it was found that the formation of sulfate complexed V(III) species is the crucial process in the precipitation reaction. The precipitation occurs through nucleation of neutral species formed through deprotonation and ion-pair formation process. However, the powder precipitate shows a multiphase nature which warrants multiple reaction pathways for precipitation reaction.

  1. Oxygen acidity of ring methoxylated 1,1-diarylalkanol radical cations bearing alpha-cyclopropyl groups. The competition between O-neophyl shift and C-cyclopropyl beta-scission in the intermediate 1,1-diarylalkoxyl radicals. (United States)

    Bietti, Massimo; Fiorentini, Simone; Pato, Iria Pèrez; Salamone, Michela


    A product and time-resolved kinetic study on the reactivity of the radical cations generated from cyclopropyl(4-methoxyphenyl)phenylmethanol (1) and cyclopropyl[bis(4-methoxyphenyl)]methanol (2) has been carried out in aqueous solution. In acidic solution, 1*+ and 2*+ display very low reactivities toward fragmentation, consistent with the presence of groups at Calpha (aryl and cyclopropyl) that after Calpha-Cbeta bond cleavage would produce relatively unstable carbon-centered radicals. In basic solution, 1*+ and 2*+ display oxygen acidity, undergoing -OH-induced deprotonation from the alpha-OH group, leading to the corresponding 1,1-diarylalkoxyl radicals 1r* and 2r*, respectively, as directly observed by time-resolved spectroscopy. The product distributions observed in the reactions of 1*+ and 2*+ under these conditions (cyclopropyl phenyl ketone, cyclopropyl(4-methoxyphenyl) ketone, and 4-methoxybenzophenone from 1*+; cyclopropyl(4-methoxyphenyl) ketone and 4,4'-dimethoxybenzophenone from 2*+) have been rationalized in terms of a water-induced competition between O-neophyl shift and C-cyclopropyl beta-scission in the intermediate 1,1-diarylalkoxyl radicals 1r* and 2r*.

  2. Does Semi-Rigid Instrumentation Using Both Flexion and Extension Dampening Spacers Truly Provide an Intermediate Level of Stabilization?

    Directory of Open Access Journals (Sweden)

    Dilip Sengupta


    Full Text Available Conventional posterior dynamic stabilization devices demonstrated a tendency towards highly rigid stabilization approximating that of titanium rods in flexion. In extension, they excessively offload the index segment, making the device as the sole load-bearing structure, with concerns of device failure. The goal of this study was to compare the kinematics and intradiscal pressure of monosegmental stabilization utilizing a new device that incorporates both a flexion and extension dampening spacer to that of rigid internal fixation and a conventional posterior dynamic stabilization device. The hypothesis was the new device would minimize the overloading of adjacent levels compared to rigid and conventional devices which can only bend but not stretch. The biomechanics were compared following injury in a human cadaveric lumbosacral spine under simulated physiological loading conditions. The stabilization with the new posterior dynamic stabilization device significantly reduced motion uniformly in all loading directions, but less so than rigid fixation. The evaluation of adjacent level motion and pressure showed some benefit of the new device when compared to rigid fixation. Posterior dynamic stabilization designs which both bend and stretch showed improved kinematic and load-sharing properties when compared to rigid fixation and when indirectly compared to existing conventional devices without a bumper.

  3. Complexation of trivalent lanthanide cations by different chelation sites of malic and tartric acid (composition, stability and probable structure

    Directory of Open Access Journals (Sweden)

    Mohammed Riri


    Full Text Available The formation of colorless gadolinium complexes (x,y,z between x gadolinium ions, y ligands and z protons of some organic acids has been studied in aqueous solution. In this work we shall present the results of investigations on the interaction of the gadolinium ion (Gd3+ with different chelation sites of malic and tartric acid formed in dilute solution for pH values between 5.50 and 7.50. The structures of these new organometallic complexes are Gd3(C4H4O52·(NO33·nH2O and Gd3(C4H4O62·(NO33·nH2O (C4H4O52-: malate ions and C4H4O62-: tartrate ions. These colorless gadolinium complexes of malate and tartrate ions have no absorption band UV–visible, the indirect photometry detection (IPD study; have identified major tri-nuclear complexes of these dicarboxylic acids, giving for these colorless complexes a (3,2,2 and (3,2,3, respectively. Composition and apparent stability constant depends on the acidity of the medium. To complement previous results and to propose probable structures for these new complexes detected in solution FT-IR and FT-Raman spectroscopy have been conducted to identify the different chelation sites for both ligands.

  4. Self-peptides with intermediate capacity to bind and stabilize MHC class I molecules may be immunogenic

    DEFF Research Database (Denmark)

    Andersen, M L M; Ruhwald, Morten; Nissen, M H;


    Thirty self-peptides were selected on the basis of their predicted binding to H-2b molecules. The binding of peptides was ascertained experimentally by biochemical (KD measurements) and cellular [major histocompatibility complex class I (MHC-I) stabilization] assays. A weak, but significant, corr...

  5. Transition-Metal Hydride Radical Cations. (United States)

    Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R


    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

  6. Studies on the inhibition of sphingosine-1-phosphate lyase by stabilized reaction intermediates and stereodefined azido phosphates. (United States)

    Sanllehí, Pol; Abad, José-Luís; Bujons, Jordi; Casas, Josefina; Delgado, Antonio


    Two kinds of inhibitors of the PLP-dependent enzyme sphingosine-1-phosphate lyase have been designed and tested on the bacterial (StS1PL) and the human (hS1PL) enzymes. Amino phosphates 1, 12, and 32, mimicking the intermediate aldimines of the catalytic process, were weak inhibitors on both enzyme sources. On the other hand, a series of stereodefined azido phosphates, resulting from the replacement of the amino group of the natural substrates with an azido group, afforded competitive inhibitors in the low micromolar range on both enzyme sources. This similar behavior represents an experimental evidence of the reported structural similarities for both enzymes at their active site level. Interestingly, the anti-isomers of the non-natural enantiomeric series where the most potent inhibitors on hS1PL.

  7. Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution. (United States)

    Lin, Yiji; Zou, Fang; Wan, Shigang; Ouyang, Jie; Lin, Lirong; Zhang, Hui


    Chiral tetrakis(β-diketonate) Ln(III) complexes Δ-[NaLa(d-hfc)(4)(CH(3)CN)] (1) and Λ-[NaLa(l-hfc)(4) (CH(3)CN)] (2) (d/l-hfc(-) = 3-heptafluo-robutylryl-(+)/(-)-camphorate) are a pair of enantiomers and crystallize in the same Sohncke space group (P2(1)2(1)2(1)) with dodecahedral (DD) geometry. Typically positive and negative exciton splitting patterns around 320 nm were observed in the solid-state circular dichroism (CD) spectra of complexes 1 and 2, which indicate that their shell configurational chiralities are Δ and Λ, respectively. The apparent bisignate couplets in the solid-state CD spectra of [CsLn(d-hfc)(4)(H(2)O)] [Ln = La (3), Yb (5)] and [CsLn(l-hfc)(4)(H(2)O)] [Ln = La (4), Yb (6)] show that they are a pair of enantiomers and their absolute configurations are denoted Δ and Λ, respectively. The crystallographic data of 5 reveals that its coordination polyhedron is the square antiprism (SAP) geometry and it undergoes a phase transition from triclinic (α phase, P1) to monoclinic (β phase, C2) upon cooling. The difference between the two phases is brought about by the temperature dependent behaviour of the coordination water molecules, but this did not affect the configurational chirality of the Δ-SAP-[Yb(d-hfc)(4)](-) moiety. Furthermore, time-dependent CD, UV-vis and (19)F NMR were applied to study the solution behavior of these complexes. It was found that the chiral-at-metal stability of the three pairs of complexes is different and affected by both the Ln(3+) and M(+) ion size. The results show that the Cs(+) cation can retain the metal center chirality and stablize the structures of [Ln(d/l-hfc)(4)](-) or the dissociated tris(d/l-hfc)Ln(III) species in solution for a longer time than that of the Na(+) cation, and it is important that the Cs(+) ion successfully lock the configurational chirality around the Yb(3+) center of the complex species in solution. This is reasoned by the short Cs(+)···FC, Cs(+)···O-Yb and Cs(+)···Yb(3

  8. Oxidation of SO2 by stabilized Criegee intermediate (sCI radicals as a crucial source for atmospheric sulfuric acid concentrations

    Directory of Open Access Journals (Sweden)

    M. Boy


    Full Text Available The effect of increased reaction rates of stabilized Criegee intermediates (sCIs with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012 increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO with SO2 according to the values recommended by Welz et al. (2012 increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

  9. Atmospheric isoprene ozonolysis: impacts of stabilized Criegee intermediate reactions with SO2, H2O and dimethyl sulfide

    Directory of Open Access Journals (Sweden)

    M. J. Newland


    Full Text Available Isoprene is the dominant global biogenic volatile organic compound (VOC emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs, which have recently been shown to be potentially important oxidants for SO2 and NO2 in the atmosphere; however the significance of this chemistry for SO2 processing (affecting sulfate aerosol and NO2 processing (affecting NOx levels depends critically upon the fate of the SCI with respect to reaction with water and decomposition. Here, we have investigated the removal of SO2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene derived SCI with H2O. Under excess SO2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (±0.03. The observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + H2O/k(SCI + SO2, of 5.4 (±0.8 × 10−5 for isoprene derived SCI. The relative rate constant for k(SCI decomposition/k(SCI + SO2 is 8.4 (±5.0 × 1010 cm−3. Uncertainties are ±2σ and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprene-derived SCIs are unlikely to make a substantial contribution to gas-phase SO2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO2 removal in the isoprene-ozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCI and DMS; the observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + DMS/k(SCI + SO2

  10. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path (United States)

    Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen


    The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550–700 °C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300–400 °C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum – most likely along Pt grain boundaries – as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum. PMID:22210951

  11. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path. (United States)

    Opitz, Alexander K; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen


    The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550-700 °C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300-400 °C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded.The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum - most likely along Pt grain boundaries - as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum.

  12. Inhibition of hypoxia-inducible factor (HIF) hydroxylases by citric acid cycle intermediates: possible links between cell metabolism and stabilization of HIF. (United States)

    Koivunen, Peppi; Hirsilä, Maija; Remes, Anne M; Hassinen, Ilmo E; Kivirikko, Kari I; Myllyharju, Johanna


    The stability and transcriptional activity of the hypoxia-inducible factors (HIFs) are regulated by two oxygen-dependent events that are catalyzed by three HIF prolyl 4-hydroxylases (HIF-P4Hs) and one HIF asparaginyl hydroxylase (FIH). We have studied possible links between metabolic pathways and HIF hydroxylases by analyzing the abilities of citric acid cycle intermediates to inhibit purified human HIF-P4Hs and FIH. Fumarate and succinate were identified as in vitro inhibitors of all three HIF-P4Hs, fumarate having K(i) values of 50-80 microM and succinate 350-460 microM, whereas neither inhibited FIH. Oxaloacetate was an additional inhibitor of all three HIF-P4Hs with K(i) values of 400-1000 microM and citrate of HIF-P4H-3, citrate being the most effective inhibitor of FIH with a K(i) of 110 microM. Culturing of cells with fumarate diethyl or dimethyl ester, or a high concentration of monoethyl ester, stabilized HIF-1alpha and increased production of vascular endothelial growth factor and erythropoietin. Similar, although much smaller, changes were found in cultured fibroblasts from a patient with fumarate hydratase (FH) deficiency and upon silencing FH using small interfering RNA. No such effects were seen upon culturing of cells with succinate diethyl or dimethyl ester. As FIH was not inhibited by fumarate, our data indicate that the transcriptional activity of HIF is quite high even when binding of the coactivator p300 is prevented. Our data also support recent suggestions that the increased fumarate and succinate levels present in the FH and succinate dehydrogenase-deficient tumors, respectively, can inhibit the HIF-P4Hs with consequent stabilization of HIF-alphas and effects on tumor pathology.

  13. Effects of Land Use Practices on the Organic Carbon Content, Cation Exchange Capacity and Aggregate Stability of Soils in the Catchment Zones

    Directory of Open Access Journals (Sweden)

    Mosayeb Heshmati


    Full Text Available Problem statement: Land use practice leads to changes in the physico-chemical properties of soils, such as Soil Organic Carbon (SOC, Cation Exchange Capacity (CEC and Soil Aggregate Stability (SAS that cause soil erosion. Approach: Merek catchment, Iran suffers from land degradation due to poor land use practice. A study was carried out with the objectives: (i to determine soil nutrient status in different agro-ecological zones in Merek catchment; and (ii to evaluate the influence of land use practices on SOC, CEC and SAS. Results: It was found that soil texture was silty and clay, while soil reaction was alkaline (pH was 7.75. The respective amount of carbonates was 32 and 36% in the top-soil and sub-soil respectively, indicating high level of alkalinity in the soils of the study area. The mean SAS of the surface soil layer for agriculture, rangeland and forest was 53, 61 and 64%, respectively with its mean in the topsoil of agriculture is significantly lower (P≤0.05 than the other zones. SOC level in the agriculture, rangeland and forest were 1.35, 1.56, 2.14 % in the topsoil and 1.03, 1.33 and 1.45%, in the subsoil of the respective areas. The results of t-test and ANOVA analyses showed that SOC means are significantly different from each other within soil depth and among agro-ecological zones. The CEC in the agriculture, rangeland and forest areas were 25.8, 24.6 and 35.1 cmolckg-1 for the top-soil and 31.1, 26.8 and 26.9 cmolckg-1 in the sub-soil, respectively. All the above changes are due to the negative effects of agricultural activities. Conclusion: Improper tillage practice (up-down the slope, conversion of the rangeland and forest to rain-fed areas, crop residue burning, over grazing and forest clearance contribute to reduction in SOC and SAS in the Merek catchment, Iran.

  14. Sequestration of Alkyltin(IV Compounds in Aqueous Solution: Formation, Stability, and Empirical Relationships for the Binding of Dimethyltin(IV Cation by N- and O-Donor Ligands

    Directory of Open Access Journals (Sweden)

    Agatino Casale


    Full Text Available The sequestering ability of polyamines and aminoacids of biological and environmental relevance (namely, ethylenediamine, putrescine, spermine, a polyallylamine, a branched polyethyleneimine, aspartate, glycinate, lysinate toward dimethyltin(IV cation was evaluated. The stability of various dimethyltin(IV / ligand species was determined in NaClaq at t=25∘C and at different ionic strengths (0.1≤I/mol L-1≤1.0, and the dependence of stability constants on this parameter was modeled by an Extended Debye-Hückel equation and by Specific ion Interaction Theory (SIT approach. At I=0.1 mol L−1, for the ML species we have log K=10.8, 14.2, 12.0, 14.7, 11.9, 7.7, 13.7, and 8.0 for ethylenediamine, putrescine, polyallylamine, spermine, polyethyleneimine, glycinate, lysinate, and aspartate, respectively. The sequestering ability toward dimethyltin(IV cation was defined by calculating the parameter pL50 (the total ligand concentration, as−log CL, able to bind 50% of metal cation, able to give an objective representation of this ability. Equations were formulated to model the dependence of pL50 on different variables, such as ionic strength and pH, and other empirical predictive relationships were also found.

  15. Advancements in Anion Exchange Membrane Cations

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, Matthew R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Long, Hai [National Renewable Energy Lab. (NREL), Golden, CO (United States); Park, Andrew M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Pivovar, Bryan S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)


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

  16. Modeling of S-Nitrosothiol-Thiol Reactions of Biological Significance: HNO Production by S-Thiolation Requires a Proton Shuttle and Stabilization of Polar Intermediates. (United States)

    Ivanova, Lena V; Cibich, Daniel; Deye, Gregory; Talipov, Marat R; Timerghazin, Qadir K


    Nitroxyl (HNO), a reduced form of the important gasotransmitter nitric oxide, exhibits its own unique biological activity. A possible biological pathway of HNO formation is the S-thiolation reaction between thiols and S-nitrosothiols (RSNOs). Our density functional theory (DFT) calculations suggested that S-thiolation proceeds through a proton transfer from the thiol to the RSNO nitrogen atom, which increases electrophilicity of the RSNO sulfur, followed by nucleophilic attack by thiol, yielding a charge-separated zwitterionic intermediate structure RSS(+) (R)N(H)O(-) (Zi), which decomposes to yield HNO and disulfide RSSR. In the gas phase, the proton transfer and the S-S bond formation are asynchronous, resulting in a high activation barrier (>40 kcal mol(-1) ), making the reaction infeasible. However, the barrier can decrease below the S-N bond dissociation energy in RSNOs (≈30 kcal mol(-1) ) upon transition into an aqueous environment that stabilizes Zi and provides a proton shuttle to synchronize the proton transfer and the S-S bond formation. These mechanistic features suggest that S-thiolation can easily lend itself to enzymatic catalysis and thus can be a possible route of endogenous HNO production.

  17. Impacts of Stabilized Criegee Intermediates, surface uptake processes and higher aromatic secondary organic aerosol yields on predicted PM2.5 concentrations in the Mexico City Metropolitan Zone (United States)

    Ying, Qi; Cureño, Iris V.; Chen, Gang; Ali, Sajjad; Zhang, Hongliang; Malloy, Meagan; Bravo, Humberto A.; Sosa, Rodolfo


    The Community Multiscale Air Quality Model (CMAQ) with the SAPRC-99 gas phase photochemical mechanism and the AERO5 aerosol module was applied to model gases and particulate matter (PM) concentrations in the Mexico City Metropolitan Zone (MCMZ) and the surrounding regions for March 2006 using the official 2006 emission inventories, along with emissions from biogenic sources, biomass burning, windblown dust, the Tula Industrial Complex and the Popocatépetl volcano. The base case model was capable of reproducing the observed hourly concentrations of O3 and attaining CO, NO2 and NOx performance similar to previous modeling studies. Although the base case model performance of hourly PM2.5 and PM10 meets the model performance criteria, under-prediction of high PM2.5 concentrations in late morning indicates that secondary PM, such as sulfate and secondary organic aerosol (SOA), might be under-predicted. Several potential pathways to increase SOA and secondary sulfate were investigated, including Stabilized Criegee Intermediates (SCIs) from ozonolysis reactions of unsaturated hydrocarbons and their reactions with SO2, the reactive uptake processes of SO2, glyoxal and methylglyoxal on particle surface and higher SOA formation due to higher mass yields of aromatic SOA precursors. Averaging over the entire episode, the glyoxal and methylglyoxal reactive uptake and higher aromatics SOA yields contribute to ∼0.9 μg m-3 and ∼1.25 μg m-3 of SOA, respectively. Episode average SOA in the MCMZ reaches ∼3 μg m-3. The SCI pathway increases PM2.5 sulfate by 0.2-0.4 μg m-3 or approximately 10-15%. The relative amount of sulfate increase due to SCI agrees with previous studies in summer eastern US. Surface SO2 uptake significantly increases sulfate concentration in MCMZ by 1-3 μg m-3 or approximately 50-60%. The higher SOA and sulfate leads to improved PM2.5 and PM10 model performance.

  18. Production of sulfonated cation-exchangers from petroleum asphaltites

    Energy Technology Data Exchange (ETDEWEB)

    Pokonova, Yu.V.; Pol' kin, G.B.; Proskuryakov, V.A.; Vinogradov, M.V.


    Continuing our studies of the preparation of products of practical value from asphaltite, a new by-product of oil refining, we obtained sulfonated cation-exchangers from a mixture of asphaltite and acid tar. It is shown that these cation-exchangers have good kinetic properties and are superior in thermal and thermohydrolytic stability to the commercial cation-exchange resin KU-2.

  19. Cationic lipids and cationic ligands induce DNA helix denaturation: detection of single stranded regions by KMnO4 probing. (United States)

    Prasad, T K; Gopal, Vijaya; Rao, N Madhusudhana


    Cationic lipids and cationic polymers are widely used in gene delivery. Using 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) as a cationic lipid, we have investigated the stability of the DNA in DOTAP:DNA complexes by probing with potassium permanganate (KMnO4). Interestingly, thymidines followed by a purine showed higher susceptibility to cationic ligand-mediated melting. Similar studies performed with other water-soluble cationic ligands such as polylysine, protamine sulfate and polyethyleneimine also demonstrated melting of the DNA but with variations. Small cations such as spermine and spermidine and a cationic detergent, cetyl trimethylammonium bromide, also rendered the DNA susceptible to modification by KMnO4. The data presented here provide direct proof for melting of DNA upon interaction with cationic lipids. Structural changes subsequent to binding of cationic lipids/ligands to DNA may lead to instability and formation of DNA bubbles in double-stranded DNA.

  20. Cation-Dependent Stabilization of Electrogenerated Naphthalene Diimide Dianions in Porous Polymer Thin Films and Their Application to Electrical Energy Storage. (United States)

    DeBlase, Catherine R; Hernández-Burgos, Kenneth; Rotter, Julian M; Fortman, David J; Abreu, Dieric dos S; Timm, Ronaldo A; Diógenes, Izaura C N; Kubota, Lauro T; Abruña, Héctor D; Dichtel, William R


    Porous polymer networks (PPNs) are attractive materials for capacitive energy storage because they offer high surface areas for increased double-layer capacitance, open structures for rapid ion transport, and redox-active moieties that enable faradaic (pseudocapacitive) energy storage. Here we demonstrate a new attractive feature of PPNs--the ability of their reduced forms (radical anions and dianions) to interact with small radii cations through synergistic interactions arising from densely packed redox-active groups, only when prepared as thin films. When naphthalene diimides (NDIs) are incorporated into PPN films, the carbonyl groups of adjacent, electrochemically generated, NDI radical anions and dianions bind strongly to K(+), Li(+), and Mg(2+), shifting the formal potentials of NDI's second reduction by 120 and 460 mV for K(+) and Li(+)-based electrolytes, respectively. In the case of Mg(2+), NDI's two redox waves coalesce into a single two-electron process with shifts of 240 and 710 mV, for the first and second reductions, respectively, increasing the energy density by over 20 % without changing the polymer backbone. In contrast, the formal reduction potentials of NDI derivatives in solution are identical for each electrolyte, and this effect has not been reported for NDI previously. This study illustrates the profound influence of the solid-state structure of a polymer on its electrochemical response, which does not simply reflect the solution-phase redox behavior of its monomers.

  1. Stabilization

    Directory of Open Access Journals (Sweden)

    Muhammad H. Al-Malack


    Full Text Available Fuel oil flyash (FFA produced in power and water desalination plants firing crude oils in the Kingdom of Saudi Arabia is being disposed in landfills, which increases the burden on the environment, therefore, FFA utilization must be encouraged. In the current research, the effect of adding FFA on the engineering properties of two indigenous soils, namely sand and marl, was investigated. FFA was added at concentrations of 5%, 10% and 15% to both soils with and without the addition of Portland cement. Mixtures of the stabilized soils were thoroughly evaluated using compaction, California Bearing Ratio (CBR, unconfined compressive strength (USC and durability tests. Results of these tests indicated that stabilized sand mixtures could not attain the ACI strength requirements. However, marl was found to satisfy the ACI strength requirement when only 5% of FFA was added together with 5% of cement. When the FFA was increased to 10% and 15%, the mixture’s strength was found to decrease to values below the ACI requirements. Results of the Toxicity Characteristics Leaching Procedure (TCLP, which was performed on samples that passed the ACI requirements, indicated that FFA must be cautiously used in soil stabilization.

  2. Computational Predictions of the Beryllium Analogue of Borole, Cp(+), and the Fluorenyl Cation: Highly Stabilized, non-Lewis Acidic Antiaromatic Ring Systems. (United States)

    Field-Theodore, Terri E; Wilson, David J D; Dutton, Jason L


    A computational study of a set of synthetically unknown beryllium-containing rings, anionic analogues of antiaromatic boroles, has been carried out to investigate their structure, stability, and potential reactivity. The results indicate that these compounds should be electronically viable (as assessed from HOMO-LUMO and singlet-triplet gaps) and therefore potential targets for synthesis. In strong contrast with boroles, these beryllium species are predicted to be not Lewis acidic but rather Lewis basic, with reactivity centered on the endocyclic Be-C bond.

  3. High redox and performance stability of layered SmBa(0.5)Sr(0.5)Co(1.5)Cu(0.5)O(5+δ) perovskite cathodes for intermediate-temperature solid oxide fuel cells. (United States)

    Jun, Areum; Shin, Jeeyoung; Kim, Guntae


    Cobalt-containing cathodes often encounter problems such as high thermal expansion coefficients (TEC) and poor stability, making them unsuitable for practical use as cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). This study focuses on the effects of Cu doping in the Co site of SmBa0.5Sr0.5Co2O5+δ in terms of structural characteristics, electrical properties, electrochemical performance, redox properties, and performance stability as an IT-SOFC cathode material. The TEC value of a SmBa0.5Sr0.5Co1.5Cu0.5O5+δ (SBSCCu50) sample is 12.8 × 10(-6) K(-1), which is lower than that (13.7 × 10(-6) K(-1)) of a SmBa0.5Sr0.5Co2O5+δ (SBSCO) sample at 700 °C. SBSCCu50 showed higher redox stability at lower p(O2) and a more stable cell power output while retaining desirable electrochemical performance, as compared with SBSCO. SBSCCu50 displayed reduced TEC values and enhanced redox and performance stability, as well as satisfactory electrical properties and electrochemical performance under typical fuel cell operating conditions. The results indicate that SBSCCu50 is a promising material as a cathode for IT-SOFCs.

  4. A study on the development of regulatory guide to stability conformation and classification criteria of low and intermediate level radioactive waste

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Geon Jae; Paek, Min Hoon; Park, Jong Gil; Han, Byeong Seop; Cheong, Jae Hak; Lee, Hae Chan; Yang, Jin Yeong; Hong, Hei Kwan; Park, Jin Baek [Korea Advanced Institute of Science and Technology, Taejon (Korea, Republic of)


    The objectives of this study are to examine basic principles and terms and to suggest and recommend definite methods and criteria necessary for the classification and stability conformation of radioactive wastes. In this study, following studies were performed : investigate the domestic regulations related with the stability conformation and classification of radioactive wastes in order to keep mutual relationship and consistency between the regulations, investigate the sources, types and characteristics of domestic radioactive wastes as a basis for this study, investigate the classification criteria and methods of others countries in a general point of view and in the view point of disposal method, select the classification criteria factors for the domestic case and general case in the both general and domestic points of view, investigate the general test items for the stability conformation of radioactive waste forms and analysis on the test items and criteria of others countries for the mined cavity disposal and shallow land disposal in the view point of disposal method, experimental leaching and immersion tests for the borate and spent resin wastes as a study on the stability conformation of waste forms, selection of acceptance criteria for the both of disposal methods in the domestic and general cases.

  5. Mesoporous TiO₂ thin films exhibiting enhanced thermal stability and controllable pore size: preparation and photocatalyzed destruction of cationic dyes. (United States)

    Wang, Jinshu; Li, Hui; Li, Hongyi; Zou, Chen; Wang, Hong; Li, Dasheng


    Ordered mesostructured TiO2 thin films were constructed through a method that combined sol-gel with evaporation-induced self-assembly (EISA). It was found that the calcination temperature, as well as the type of block copolymer, could vary the TiO2 mesoporous structure. Based on tension stress calculated by the surface energy of crystallites and the compression calculated by interface energy between the crystallites, the thermodynamic study for the sample had been carried out and the critical crystallite size expression of the mesoporous film was presented for the prediction of the thermal stability of the mesoporous structure at high temperature. It was also found that varying the mass ratio of templating agent to inorganic precursor could adjust the pore size of mesoporous TiO2. The pore size regulating mechanism had been discussed. The sample calcined at 450-500 °C, which had a higher specific surface area and larger pore size, exhibited higher photocatalyzed destruction capability of Methylene Blue.

  6. Interaction between anions and cationic metal complexes containing tridentate ligands with exo-C-H groups: complex stability and hydrogen bonding. (United States)

    Martínez-García, Héctor; Morales, Dolores; Pérez, Julio; Puerto, Marcos; del Río, Ignacio


    [Re(CO)3 ([9]aneS3 )][BAr'4 ] (1), prepared by reaction of ReBr(CO)5 , 1,4,7-trithiacyclononane ([9]aneS3 ) and NaBAr'4 , forms stable, soluble supramolecular adducts with chloride (2), bromide, methanosulfonate (3) and fluoride (4) anions. These new species were characterized by IR, NMR spectroscopy and, for 2 and 3, also by X-ray diffraction. The results of the solid state structure determinations indicate the formation of CH⋅⋅⋅X hydrogen bonds between the anion (X) and the exo-CH groups of the [9]aneS3 ligand, in accord with the relatively large shifts found by (1) H NMR spectroscopy in dichloromethane solution for those hydrogens. The stability of the chloride adduct contrasts with the lability of the [9]aneS3 ligand in allyldicarbonyl molybdenum complexes recently studied by us. With fluoride, in dichloromethane solution, a second, minor neutral dimeric species 5 is formed in addition to 4. In 4, the deprotonation of a CH group of the [9]aneS3 ligand, accompanied by CS bond cleavage and dimerization, afforded 5, featuring bridging thiolates. Compounds [Mo(η(3) -methallyl)(CO)2 (TpyN)][BAr'4 ] (6) and [Mo(η(3) -methallyl)(CO)2 (TpyCH)][BAr'4 ] (7) were synthesized by the reactions of [MoCl(η(3) -methallyl)(CO)2 (NCMe)2 ], NaBAr'4 and tris(2-pyridyl)amine (TpyN) or tris(2-pyridyl)methane (TpyCH) respectively, and characterized by IR and (1) H and (13) C NMR spectroscopy in solution, and by X-ray diffraction in the solid state. Compound 6 undergoes facile substitution of one of the 2-pyridyl groups by chloride, bromide, and methanosulfonate anions. Stable supramolecular adducts were formed between 7 and chloride, bromide, iodide, nitrate, and perrhenate anions. The solid state structures of these adducts (12-16) were determined by X-ray diffraction. Binding constants in dichloromethane were calculated from (1) H NMR titration data for all the new supramolecular adducts. The signal of the bridgehead CH group is the one that undergoes a

  7. Cationic hetero diffusion and mechanical properties of yttria-stabilized zirconia: influence of irradiation; Heterodiffusion cationique et proprietes mecaniques de la zircone stabilisee a l'oxyde d'yttrium: influence de l'irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Menvie Bekale, V


    Cubic yttria-stabilized zirconia (YSZ) is a promising material as target for the transmutation of radioactive waste. In this context, the present work is dedicated to the study of the atomic transport and the mechanical properties of this ceramic, as well as the influence of irradiation on these properties. The preliminary step concerns the synthesis of YSZ cubic zirconia ceramic undoped and doped with rare earths to form homogeneous Ce-YSZ or Gd-YSZ solid solutions with the highest density. The diffusion experiments of Ce and Gd in YSZ or Ce-YSZ were performed in air from 900 to 1400 C, and the depth profiles were established by SIMS. The bulk diffusion decreases when the ionic radius of diffusing element increases. The comparison with literature data of activation energies for bulk diffusion suggests that the cationic diffusion occurs via a vacancy mechanism. The diffusion results of Ce in YSZ irradiated with 4 or 20 MeV Au ions show a bulk diffusion slowing-down at 1000 and 1100 C when the radiation damage becomes important (30 dpa). The mechanical properties of YSZ ceramics irradiated with 944 MeV Pb ions and non irradiated samples were studied by Vickers micro indentation and Berkovitch nano indentation techniques. The hardness of the material increases when the average grain size decreases. Furthermore, the hardness and the toughness increase with irradiation fluence owing to the occurrence of compressive residual stresses in the irradiated area. (author)

  8. Solvent-dependent dihydrogen/dihydride stability for [Mo(CO)(Cp*)H(2)(PMe(3))(2)](+)[BF(4)](-) determined by multiple solvent...anion...cation non-covalent interactions. (United States)

    Dub, Pavel A; Belkova, Natalia V; Filippov, Oleg A; Daran, Jean-Claude; Epstein, Lina M; Lledós, Agustí; Shubina, Elena S; Poli, Rinaldo


    Low-temperature (200 K) protonation of [Mo(CO)(Cp*)H(PMe(3))(2)] (1) by Et(2)OHBF(4) gives a different result depending on a subtle solvent change: The dihydrogen complex [Mo(CO)(Cp*)(eta(2)-H(2))(PMe(3))(2)](+) (2) is obtained in THF, whereas the tautomeric classical dihydride [Mo(CO)(Cp*)(H)(2)(PMe(3))(2)](+) (3) is the only observable product in dichloromethane. Both products were fully characterised (nu(CO) IR; (1)H, (31)P, (13)C NMR spectroscopies) at low temperature; they lose H(2) upon warming to 230 K at approximately the same rate (ca. 10(-3) s(-1)), with no detection of the non-classical form in CD(2)Cl(2), to generate [Mo(CO)(Cp*)(FBF(3))(PMe(3))(2)] (4). The latter also slowly decomposes at ambient temperature. One of the decomposition products was crystallised and identified by X-ray crystallography as [Mo(CO)(Cp*)(FHFBF(3))(PMe(3))(2)] (5), which features a neutral HF ligand coordinated to the transition metal through the F atom and to the BF(4) (-) anion through a hydrogen bond. The reason for the switch in relative stability between 2 and 3 was probed by DFT calculations based on the B3LYP and M05-2X functionals, with inclusion of anion and solvent effects by the conductor-like polarisable continuum model and by explicit consideration of the solvent molecules. Calculations at the MP4(SDQ) and CCSD(T) levels were also carried out for calibration. The calculations reveal the key role of non-covalent anion-solvent interactions, which modulate the anion-cation interaction ultimately altering the energetic balance between the two isomeric forms.

  9. 阳离子聚合物粘土稳定剂的合成及性能研究%Preparation and evaluation of the clay stabilizer of cationic polymerization

    Institute of Scientific and Technical Information of China (English)

    李丛妮; 雷珂


    以二甲胺、环氧氯丙烷为原料,通过缩合聚合反应,合成了阳离子有机聚合物粘土稳定剂.考察了原料配比、反应温度、反应时间对防膨率的影响.结果表明,最佳合成工艺条件为:环氧氯丙烷与二甲胺的摩尔配比为1∶1.2,反应时间5h,反应温度60℃.粘土稳定剂用量2.0%时,防膨率为87.5%;与KCl或NH4Cl以1∶1复配,用量为4%时,防膨率分别为94.9%,93.2%.粘土稳定剂用量2.0%时,第1次和第2次岩屑回收率分别为82.16%,79.49%;2%聚合物+1%KCl+ 1%NH4Cl三元复配,第1次和第2次回收率分别为89.66%,86.41%.%Dimethylamine and epichlorohydrin as raw materials,the organic cationic polymer clay stabilizer was synthesized by condensation polymerization reaction.The effects of raw materials molar ratio,reaction temperature and reaction time on anti-swelling rate has been discussed.The results indicated that the optimal synthetic conditions were found as follows:epichlorohydrin and dimethylamine molar ratio 1 ∶ 1.2,the reaction time 5 h,reaction temperature 60 ℃.The amount of clay stabilizer 2.0%,the anti-swelling rate 87.5%,the first and second debris recovery rate were 82.16% and 79.49%,the compound of KCl ∶ NH4Cl =1 ∶ 1,the amount was 4%,the anti-swelling rate were 94.9% and 93.2% ; the ternary compound of 2% polymer + 1% KCl + 1% NH4Cl,the first and second recovery rate reached 89.66% and 86.41%.

  10. Surface Intermediate Zone of Submerged Turbulent Buoyant Jet in Current

    DEFF Research Database (Denmark)

    Chen, H. B.; Larsen, Torben


    This paper deals with the intermediate zone between the jet and plume stages of a submerged buoyant discharge from sea outfall in current. The stability criteria, plume width and height after the intermediate zone and the dilution within the intermediate region have been studied theoretically...

  11. Degradation Mechanism of Cationic Red X-GRL by Ozonation

    Institute of Scientific and Technical Information of China (English)

    Wei Rong ZHAO; Xin Hua XU; Hui Xiang SHI; Da Hui WANG


    The degradation mechanism of Cationic Red X-GRL was investigated when the intermediates, the nitrate ion and the pH were analyzed in the ozonation. The degradation of the Cationic Red X-GRL includes the de-auxochrome stage, the decolour stage, and the decomposition of fragment stage. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one becomes the form of an amine compound, and the rest four are transformed into two molecules of nitrogen. In the course of the ozonation of Cationic Red X-GRL, the direct attack of ozone is the main decolour effect.

  12. DFT study on the cycloreversion of thietane radical cations. (United States)

    Domingo, Luis R; Pérez-Ruiz, Raúl; Argüello, Juan E; Miranda, Miguel A


    The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4+2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b(•+) is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b(•+) (ii). Calculations support that 1a(•+) follows reaction pathway ii (leading to the formal [4+2] cycloadducts 5a). By contrast, 1b(•+) follows pathway i, leading to trans-stilbene radical cation (2b(•+)) and thiobenzophenone.

  13. Anionic Polyelectrolyte-Cationic Surfactant Interactions in Aqueous Solutions and Foam Films Stability Interactions entre polyélectrolytes anioniques et tensioactifs cationiques en solutions aqueuses et stabilité des films de mousses

    Directory of Open Access Journals (Sweden)

    Langevin D.


    Full Text Available The objective of this work is to study polymer/surfactant interactions in aqueous solution and at the air/water interface. These interations are involved in many physicochemical phenomena, such as colloidal stabilization and wettability which are of major importance in oil application as for exemple drilling muds. More precisely, we have attempted to characterize interactions between a non surface active anionic copolymer (acrylamide/acrylamide sulfonate and an oppositely charged cationic surfactant (C12 TAB. Our results show a synergestic surface tension lowering (coadsorption at extremely low surfactant concentrations (10 to the power of (-3 to 10 to the power of (-1 CMC. At higher concentrations, namely above the so called Critical Aggregation Concentration (CAC, polymer-surfactant complexes form in the bulk and the macromolecules precipitate out of the solution. Foam films made from these mixed solutions are stable while C12TAB films are unstable. Disjoining pressure measurements on mixed films with surfactant concentration two orders of magnitude below the CAC show the existence of long range repulsive forces and a discrete film thickness transition. At the CAC, we obtain mixed films with gel-like networks that are strongly affected by the film thinning rate. L'objectif de cette étude est d'étudier les interactions polymère/tensioactif en solution aqueuse et à l'interface eau/air. Ces interactions interviennent dans de nombreux phénomènes physico-chimiques tels que la stabilisation de suspensions colloïdales et la mouillabilité qui sont d'une importance majeure dans les applications pétrolières comme, par exemple, les boues de forage. Plus précisément, nous avons essayé de caractériser les interactions entre un copolymère anionique n'ayant pas d'activité de surface (acrylamide/acrylamide sulfoné avec un tensioactif de charge opposée cationique (C12TAB. Nos résultats montrent une diminution synergique de la tension

  14. Cation exchange properties of zeolites in hyper alkaline aqueous media. (United States)

    Van Tendeloo, Leen; de Blochouse, Benny; Dom, Dirk; Vancluysen, Jacqueline; Snellings, Ruben; Martens, Johan A; Kirschhock, Christine E A; Maes, André; Breynaert, Eric


    Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media.

  15. Stabilization of noncondensed (As(III)S3)(3-) anions by coordinating to [Mn(II)(phen)](2+) complex cations: a mixed-valent thioarsenate (III, V) {[Mn(phen)]3(As(V)S4)(As(III)S3)}(n)·nH2O showing the coexistence of antiferromagnetic order, photoluminescence, and nonlinear optical properties. (United States)

    Liu, Guang-Ning; Jiang, Xiao-Ming; Wu, Mei-Feng; Wang, Guan-E; Guo, Guo-Cong; Huang, Jin-Shun


    A novel one-dimensional (1-D) mixed-valent thioarsenate (III, V), {[Mn(phen)](3)(As(V)S(4))(As(III)S(3))}(n)·nH(2)O (1), with a noncentrosymmetric (NCS) polar packing arrangement has been obtained under solvothermal conditions. The noncondensed (As(III)S(3))(3-) anion in 1 is stabilized by coordinating to [Mn(II)(phen)](2+) complex cations and exhibits an unprecedented μ(3)-1,2κS:2,3κS':3κS'' linkage mode. Compound 1 represents the first example of the stabilization of noncondensed (MQ(3))(3-) (M = As, Sb; Q = S, Se) species only in the coordination of TM(II) complex cations (TM = transition-metal) and the first observation of the coexistence of the (As(V)S(4))(3-) tetrahedron and the noncondensed (As(III)S(3))(3-) pyramid in a single compound. Of particular interest, compound 1 is also an antiferromagnet with T(N) = 31 K, and exhibits photoluminescence (PL) with a maximum emission at about 438 nm and a second harmonic generation (SHG) response.

  16. Branching of keratin intermediate filaments. (United States)

    Nafeey, Soufi; Martin, Ines; Felder, Tatiana; Walther, Paul; Felder, Edward


    Keratin intermediate filaments (IFs) are crucial to maintain mechanical stability in epithelial cells. Since little is known about the network architecture that provides this stiffness and especially about branching properties of filaments, we addressed this question with different electron microscopic (EM) methods. Using EM tomography of high pressure frozen keratinocytes, we investigated the course of several filaments in a branching of a filament bundle. Moreover we found several putative bifurcations in individual filaments. To verify our observation we also visualized the keratin network in detergent extracted keratinocytes with scanning EM. Here bifurcations of individual filaments could unambiguously be identified additionally to bundle branchings. Interestingly, identical filament bifurcations were also found in purified keratin 8/18 filaments expressed in Escherichia coli which were reassembled in vitro. This excludes that an accessory protein contributes to the branch formation. Measurements of the filament cross sectional areas showed various ratios between the three bifurcation arms. This demonstrates that intermediate filament furcation is very different from actin furcation where an entire new filament is attached to an existing filament. Instead, the architecture of intermediate filament bifurcations is less predetermined and hence consistent with the general concept of IF formation.

  17. Capillary electrophoresis analysis of inorganic cations in post-blast residue extracts applying a guanidinium-based electrolyte and bilayer-coated capillaries. (United States)

    Sarazin, Cédric; Delaunay, Nathalie; Costanza, Christine; Eudes, Véronique; Gareil, Pierre


    A new CE method was developed for the identification and quantitation of inorganic cations in post-blast residues. The simultaneous analysis in 20 min total runtime of eight cations in post-blast residues (ammonium, potassium, monomethylammonium, calcium, sodium, magnesium, strontium), plus lithium cation as the internal reference, was carried out with a BGE involving a non-CMR (carcinogenic, mutagenic, and harmful to reproduction) chromophore (guanidinium cation) and a double-layer modified capillary (hexadimethrine bromide/polyvinylsulfonate). A study of UV detection conditions using guanidinium ion as the probe led us to set the analysis and reference wavelengths and their associated bandwidths as well as the probe concentration fixed at 15 mM. The successive multiple ionic-polymer layer approach limited the cation adsorption on capillary wall and improved the EOF stability. These caused a significant improvement in method repeatability. Intermediate precisions were 2.4% for corrected areas and 1.3% for normalized migration times. Limits of detection close to 1 mg/L for all cations were obtained. The matrix effects were studied with chemometric approach for different matrices representative of those collected after explosion. Tests with blank matrix extracts of soil, cloth, and with simulated matrix extract containing 800 mg/L Ca²⁺ and 500 mg/L Fe²⁺ were carried out and no significant matrix effects were observed. Finally, analyses of real residues collected after cash dispenser and homemade firework explosions demonstrate excellent correlation between the CE results and those obtained with the ion chromatography method used routinely.

  18. Simplifying biochemical models with intermediate species

    DEFF Research Database (Denmark)

    Feliu, Elisenda; Wiuf, Carsten


    canonical model that characterizes crucial dynamical properties, such as mono- and multistationarity and stability of steady states, of all models in the class. We show that if the core model does not have conservation laws, then the introduction of intermediates does not change the steady...... techniques, we study systematically the effects of intermediate, or transient, species in biochemical systems and provide a simple, yet rigorous mathematical classification of all models obtained from a core model by including intermediates. Main examples include enzymatic and post-translational modification...... systems, where intermediates often are considered insignificant and neglected in a model, or they are not included because we are unaware of their existence. All possible models obtained from the core model are classified into a finite number of classes. Each class is defined by a mathematically simple...

  19. Morphological Analysis of Effect of Metal Cations on Structural Stability of Phosphatidylcholine/Cholesterol Liposomes%金属阳离子影响卵磷脂-胆固醇脂质体结构稳定性的形态学分析

    Institute of Scientific and Technical Information of China (English)

    张诗音; 肖启; 寇贝贝; 朱杰; 王国栋


    This article showed primary study and analyses on the impacts done by the metal cations to the stability of liposomes which are made of cholesterol and lecithin.Using images given by atomic force mi-croscope,the interaction mechanism in nanoscale was investigated and conducted by methods combining basic principles of thermodynamics,electrostatics and colloid science.The study illustrated that the pro-portion of cholesterol significantly influenced the fluidity and stability of the lipid membrane.Meanwhile, it also indicated that the cations could influence these liposomes both on the ability of assembling them-selves and on the thermodynamic stability by interactions with polar heads of the phospholipid molecules.%以胆固醇和卵磷脂二元脂质体为研究模型,采用原子力显微镜显微技术,结合基本的热力学、静电力学与胶体科学原理,从微观成像的结果追溯和推测更微观层面上的作用机制,对金属阳离子对脂质体结构稳定性形态学特征进行了初步分析。研究发现,胆固醇的含量对脂膜的流动性和稳定性有着明显的影响,而金属阳离子可与磷脂分子极性头基发生作用,从而影响到脂质体的组装能力以及脂质体胶体系统的热力学稳定性。

  20. Bacterial intermediate filaments

    DEFF Research Database (Denmark)

    Charbon, Godefroid; Cabeen, M.; Jacobs-Wagner, C.


    Crescentin, which is the founding member of a rapidly growing family of bacterial cytoskeletal proteins, was previously proposed to resemble eukaryotic intermediate filament (IF) proteins based on structural prediction and in vitro polymerization properties. Here, we demonstrate that crescentin...

  1. Intermediate algebra a textworkbook

    CERN Document Server

    McKeague, Charles P


    Intermediate Algebra: A Text/Workbook, Second Edition focuses on the principles, operations, and approaches involved in intermediate algebra. The publication first takes a look at basic properties and definitions, first-degree equations and inequalities, and exponents and polynomials. Discussions focus on properties of exponents, polynomials, sums, and differences, multiplication of polynomials, inequalities involving absolute value, word problems, first-degree inequalities, real numbers, opposites, reciprocals, and absolute value, and addition and subtraction of real numbers. The text then ex

  2. Intermediate algebra & analytic geometry

    CERN Document Server

    Gondin, William R


    Intermediate Algebra & Analytic Geometry Made Simple focuses on the principles, processes, calculations, and methodologies involved in intermediate algebra and analytic geometry. The publication first offers information on linear equations in two unknowns and variables, functions, and graphs. Discussions focus on graphic interpretations, explicit and implicit functions, first quadrant graphs, variables and functions, determinate and indeterminate systems, independent and dependent equations, and defective and redundant systems. The text then examines quadratic equations in one variable, system

  3. C [bond] H activation by cationic platinum(II) complexes: ligand electronic and steric effects. (United States)

    Zhong, H Annita; Labinger, Jay A; Bercaw, John E


    A series of bis(aryl)diimine-ligated methyl complexes of Pt(II) with various substituted aryl groups has been prepared. The cationic complexes [(ArN=CR [bond] CR=NAr)PtMe(L)](+)[BF(4)](-) (Ar = aryl; R = H, CH(3); L = water, trifluoroethanol) react smoothly with benzene at approximately room temperature in trifluoroethanol solvent to yield methane and the corresponding phenyl Pt(II) cations, via Pt(IV)-methyl-phenyl-hydrido intermediates. The reaction products of methyl-substituted benzenes suggest an inherent reactivity preference for aromatic over benzylic C [bond] H activation, which can however be overridden by steric effects. For the reaction of benzene with cationic Pt(II) complexes bearing 3,5-disubstituted aryl diimine ligands, the rate-determining step is C [bond] H activation, whereas for the more sterically crowded analogues with 2,6-dimethyl-substituted aryl groups, benzene coordination becomes rate-determining. This switch is manifested in distinctly different isotope scrambling and kinetic deuterium isotope effect patterns. The more electron-rich the ligand is, as assayed by the CO stretching frequency of the corresponding carbonyl cationic complex, the faster the rate of C [bond] H activation. Although at first sight this trend appears to be at odds with the common description of this class of reaction as electrophilic, the fact that the same trend is observed for the two different series of complexes, which have different rate-determining steps, suggests that this finding does not reflect the actual C [bond] H activation process, but rather reflects only the relative ease of benzene displacing a ligand to initiate the reaction; that is, the change in rates is mostly due to a ground-state effect. The stability of the aquo complex ground state in equilibrium with the solvento complex increases as the diimine ligand is made more electron-withdrawing. Several lines of evidence, including the mechanism of degenerate acetonitrile exchange for the methyl

  4. Radical Addition to Iminium Ions and Cationic Heterocycles

    Directory of Open Access Journals (Sweden)

    Johannes Tauber


    Full Text Available Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta reaction, and the Knabe rearrangement will be discussed along with transition metal and photoredox catalysis or electrochemical methods to generate the odd-electron species.

  5. Aggregate Formed by a Cationic Fluorescence Probe

    Institute of Scientific and Technical Information of China (English)

    TIAN, Juan; SANG, Da-Yong; JI, Guo-Zhen


    The aggregation behavior of a cationic fluorescence probe 10-(4,7,10,13,16-pentaoxa-1-azacyclooctadecyl-methyl)anthracen-9-ylmethyl dodecanoate (1) was observed and studied by a fluorescence methodology in acidic and neutral conditions. By using the Py scale, differences between simple aggregates and micelles have been discussed. The stability of simple aggregates was discussed in terms of hydrophobic interaction and electrostatic repulsion. The absence of excimer emission of the anthrancene moiety of probe 1 in neutral condition was attributed to the photoinduced electron transfer mechanism instead of photodimerization.

  6. Cell volume-regulated cation channels. (United States)

    Wehner, Frank


    Considering the enormous turnover rates of ion channels when compared to carriers it is quite obvious that channel-mediated ion transport may serve as a rapid and efficient mechanism of cell volume regulation. Whenever studied in a quantitative fashion the hypertonic activation of non-selective cation channels is found to be the main mechanism of regulatory volume increase (RVI). Some channels are inhibited by amiloride (and may be related to the ENaC), others are blocked by Gd(3) and flufenamate (and possibly linked to the group of transient receptor potential (TRP) channels). Nevertheless, the actual architecture of hypertonicity-induced cation channels remains to be defined. In some preparations, hypertonic stress decreases K(+) channel activity so reducing the continuous K(+) leak out of the cell; this is equivalent to a net gain of cell osmolytes facilitating RVI. The hypotonic activation of K(+) selective channels appears to be one of the most common principles of regulatory volume decrease (RVD) and, in most instances, the actual channels involved could be identified on the molecular level. These are BKCa (or maxi K(+)) channels, IK(Ca) and SK(Ca) channels (of intermediate and small conductance, respectively), the group of voltage-gated (Kv) channels including their Beta (or Kv ancilliary) subunits, two-pore K(2P) channels, as well as inwardly rectifying K(+) (Kir) channels (also contributing to K(ATP) channels). In some cells, hypotonicity activates non-selective cation channels. This is surprising, at first sight, because of the inside negative membrane voltage and the sum of driving forces for Na(+) and K(+) diffusion across the cell membrane rather favouring net cation uptake. Some of these channels, however, exhibit a P(K)/P(Na) significantly higher than 1, whereas others are Ca(++) permeable linking hypotonic stress to the activation of Ca(++) dependent ion channels. In particular, the latter holds for the group of TRPs which are specialised in the

  7. Theoretical Studies on the Interactions of Cations with Diazine

    Institute of Scientific and Technical Information of China (English)

    CHEN Xing; WU Wen-Peng; ZHANG Jing-Lai; CAO Ze-Xing


    Density functional theory and MP2 calculations have been used to determine the geometries, stabilities, binding energies, and dissociative properties of cation-diazine complexes Mn+-C4H4N2 (Mn+ = Li+, B+, Al+, Be2+, Mg2+, Ca2+). The calculated results indicate that most complexes are stable except the π complexes of Ca2+-pyridazine, Ca2+-pyrazine, Al+-pyrimidine and Al+-pyrimidine. The σ complexes are generally much more stable than their π counterparts. Among the π complexes, the cation-pyrazine π complexes have slightly higher stability. The nature of the ion-molecule interactions has been discussed by the natural bond orbital analysis and frontier molecular orbital interactions. In these σ complexes, there is stronger covalent interaction between B+ and diazine. In the selected π complexes, B+ and Be2+ have stronger covalent interaction with diazine, while the other cations mainly have electrostatic interaction with diazine.

  8. Intermediate-energy nuclear chemistry workshop

    Energy Technology Data Exchange (ETDEWEB)

    Butler, G.W.; Giesler, G.C.; Liu, L.C.; Dropesky, B.J.; Knight, J.D.; Lucero, F.; Orth, C.J.


    This report contains the proceedings of the LAMPF Intermediate-Energy Nuclear Chemistry Workshop held in Los Alamos, New Mexico, June 23-27, 1980. The first two days of the Workshop were devoted to invited review talks highlighting current experimental and theoretical research activities in intermediate-energy nuclear chemistry and physics. Working panels representing major topic areas carried out indepth appraisals of present research and formulated recommendations for future research directions. The major topic areas were Pion-Nucleus Reactions, Nucleon-Nucleus Reactions and Nuclei Far from Stability, Mesonic Atoms, Exotic Interactions, New Theoretical Approaches, and New Experimental Techniques and New Nuclear Chemistry Facilities.

  9. Mobile communication and intermediality

    DEFF Research Database (Denmark)

    Helles, Rasmus


    The article argues the importance of intermediality as a concept for research in mobile communication and media. The constant availability of several, partially overlapping channels for communication (texting, calls, email, Facebook, etc.) requires that we adopt an integrated view of the various...... communicative affordances of mobile devices in order to understand how people choose between them for different purposes. It is argued that mobile communication makes intermediality especially central, as the choice of medium is detached from the location of stationary media and begins to follow the user across...




  11. The diastereoselective synthesis of octahedral cationic iridium hydride complexes with a stereogenic metal centre. (United States)

    Humbert, Nicolas; Mazet, Clément


    We report herein the highly diastereoselective synthesis of octahedral cationic Ir(iii) hydride complexes with a stereogenic metal centre following various strategies. The configurational stability of these compounds has also been investigated.

  12. Circular dichroism and fluorescence spectroscopy of cysteinyl-tRNA synthetase from Halobacterium salinarum ssp. NRC-1 demonstrates that group I cations are particularly effective in providing structure and stability to this halophilic protein.

    Directory of Open Access Journals (Sweden)

    Christopher J Reed

    Full Text Available Proteins from extremophiles have the ability to fold and remain stable in their extreme environment. Here, we investigate the presence of this effect in the cysteinyl-tRNA synthetase from Halobacterium salinarum ssp. NRC-1 (NRC-1, which was used as a model halophilic protein. The effects of salt on the structure and stability of NRC-1 and of E. coli CysRS were investigated through far-UV circular dichroism (CD spectroscopy, fluorescence spectroscopy, and thermal denaturation melts. The CD of NRC-1 CysRS was examined in different group I and group II chloride salts to examine the effects of the metal ions. Potassium was observed to have the strongest effect on NRC-1 CysRS structure, with the other group I salts having reduced strength. The group II salts had little effect on the protein. This suggests that the halophilic adaptations in this protein are mediated by potassium. CD and fluorescence spectra showed structural changes taking place in NRC-1 CysRS over the concentration range of 0-3 M KCl, while the structure of E. coli CysRS was relatively unaffected. Salt was also shown to increase the thermal stability of NRC-1 CysRS since the melt temperature of the CysRS from NRC-1 was increased in the presence of high salt, whereas the E. coli enzyme showed a decrease. By characterizing these interactions, this study not only explains the stability of halophilic proteins in extremes of salt, but also helps us to understand why and how group I salts stabilize proteins in general.

  13. Intermediate Q from soluble methane monooxygenase hydroxylates the mechanistic substrate probe norcarane: evidence for a stepwise reaction. (United States)

    Brazeau, B J; Austin, R N; Tarr, C; Groves, J T; Lipscomb, J D


    Norcarane is a valuable mechanistic probe for enzyme-catalyzed hydrocarbon oxidation reactions because different products or product distributions result from concerted, radical, and cation based reactions. Soluble methane monooxygenase (sMMO) from Methylosinus trichosporium OB3b catalyzes the oxidation of norcarane to afford 3-hydroxymethylcyclohexene and 3-cycloheptenol, compounds characteristic of radical and cationic intermediates, respectively, in addition to 2- and 3-norcaranols. Past single turnover transient kinetic studies have identified several optically distinct intermediates from the catalytic cycle of the hydroxylase component of sMMO. Thus, the reaction between norcarane and key reaction intermediates can be directly monitored. The presence of norcarane increases the rate of decay of only one intermediate, the high-valent bis-mu-oxo Fe(IV)(2) cluster-containing species compound Q, showing that it is responsible for the majority of the oxidation chemistry. The observation of products from both radical and cationic intermediates from norcarane oxidation catalyzed by sMMO is consistent with a mechanism in which an initial substrate radical intermediate is formed by hydrogen atom abstraction. This intermediate then undergoes either oxygen rebound, intramolecular rearrangement followed by oxygen rebound, or loss of a second electron to yield a cationic intermediate to which OH(-) is transferred. The estimated lower limit of 20 ps for the lifetime of the putative radical intermediate is in accord with values determined from previous studies of sterically hindered sMMO probes.

  14. Complexation Between Cationic Diblock Copolymers and Plasmid DNA (United States)

    Jung, Seyoung; Reineke, Theresa; Lodge, Timothy

    Deoxyribonucleic acids (DNA), as polyanions, can spontaneously bind with polycations to form polyelectrolyte complexes. When the polycation is a diblock copolymer with one cationic block and one uncharged hydrophilic block, the polyelectrolyte complexes formed with plasmid DNA (pDNA) are often colloidally stable, and show great promise in the field of polymeric gene therapy. While the resulting properties (size, stability, and toxicity to biological systems) of the complexes have been studied for numerous cationic diblocks, the fundamentals of the pDNA-diblock binding process have not been extensively investigated. Herein, we report how the cationic block content of a diblock influences the pDNA-diblock interactions. pDNA with 7164 base pairs and poly(2-deoxy-2-methacrylamido glucopyranose)-block-poly(N-(2-aminoethyl) methacrylamide) (PMAG-b-PAEMA) are used as the model pDNA and cationic diblock, respectively. To vary the cationic block content, two PMAG-b-PAEMA copolymers with similar PMAG block lengths but distinct PAEMA block lengths and a PAEMA homopolymer are utilized. We show that the enthalpy change from pDNA-diblock interactions is dependent on the cationic diblock composition, and is closely associated with both the binding strength and the pDNA tertiary structure.

  15. Synthetic cation-selective nanotube: Permeant cations chaperoned by anions (United States)

    Hilder, Tamsyn A.; Gordon, Dan; Chung, Shin-Ho


    The ability to design ion-selective, synthetic nanotubes which mimic biological ion channels may have significant implications for the future treatment of bacteria, diseases, and as ultrasensitive biosensors. We present the design of a synthetic nanotube made from carbon atoms that selectively allows monovalent cations to move across and rejects all anions. The cation-selective nanotube mimics some of the salient properties of biological ion channels. Before practical nanodevices are successfully fabricated it is vital that proof-of-concept computational studies are performed. With this in mind we use molecular and stochastic dynamics simulations to characterize the dynamics of ion permeation across a single-walled (10, 10), 36 Å long, carbon nanotube terminated with carboxylic acid with an effective radius of 5.08 Å. Although cations encounter a high energy barrier of 7 kT, its height is drastically reduced by a chloride ion in the nanotube. The presence of a chloride ion near the pore entrance thus enables a cation to enter the pore and, once in the pore, it is chaperoned by the resident counterion across the narrow pore. The moment the chaperoned cation transits the pore, the counterion moves back to the entrance to ferry another ion. The synthetic nanotube has a high sodium conductance of 124 pS and shows linear current-voltage and current-concentration profiles. The cation-anion selectivity ratio ranges from 8 to 25, depending on the ionic concentrations in the reservoirs.

  16. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong


    and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...

  17. The Intermediate Neutrino Program

    CERN Document Server

    Adams, C; Ankowski, A M; Asaadi, J A; Ashenfelter, J; Axani, S N; Babu, K; Backhouse, C; Band, H R; Barbeau, P S; Barros, N; Bernstein, A; Betancourt, M; Bishai, M; Blucher, E; Bouffard, J; Bowden, N; Brice, S; Bryan, C; Camilleri, L; Cao, J; Carlson, J; Carr, R E; Chatterjee, A; Chen, M; Chen, S; Chiu, M; Church, E D; Collar, J I; Collin, G; Conrad, J M; Convery, M R; Cooper, R L; Cowen, D; Davoudiasl, H; De Gouvea, A; Dean, D J; Deichert, G; Descamps, F; DeYoung, T; Diwan, M V; Djurcic, Z; Dolinski, M J; Dolph, J; Donnelly, B; Dwyer, D A; Dytman, S; Efremenko, Y; Everett, L L; Fava, A; Figueroa-Feliciano, E; Fleming, B; Friedland, A; Fujikawa, B K; Gaisser, T K; Galeazzi, M; Galehouse, D C; Galindo-Uribarri, A; Garvey, G T; Gautam, S; Gilje, K E; Gonzalez-Garcia, M; Goodman, M C; Gordon, H; Gramellini, E; Green, M P; Guglielmi, A; Hackenburg, R W; Hackenburg, A; Halzen, F; Han, K; Hans, S; Harris, D; Heeger, K M; Herman, M; Hill, R; Holin, A; Huber, P; Jaffe, D E; Johnson, R A; Joshi, J; Karagiorgi, G; Kaufman, L J; Kayser, B; Kettell, S H; Kirby, B J; Klein, J R; Kolomensky, Yu G; Kriske, R M; Lane, C E; Langford, T J; Lankford, A; Lau, K; Learned, J G; Ling, J; Link, J M; Lissauer, D; Littenberg, L; Littlejohn, B R; Lockwitz, S; Lokajicek, M; Louis, W C; Luk, K; Lykken, J; Marciano, W J; Maricic, J; Markoff, D M; Caicedo, D A Martinez; Mauger, C; Mavrokoridis, K; McCluskey, E; McKeen, D; McKeown, R; Mills, G; Mocioiu, I; Monreal, B; Mooney, M R; Morfin, J G; Mumm, P; Napolitano, J; Neilson, R; Nelson, J K; Nessi, M; Norcini, D; Nova, F; Nygren, D R; Gann, G D Orebi; Palamara, O; Parsa, Z; Patterson, R; Paul, P; Pocar, A; Qian, X; Raaf, J L; Rameika, R; Ranucci, G; Ray, H; Reyna, D; Rich, G C; Rodrigues, P; Romero, E Romero; Rosero, R; Rountree, S D; Rybolt, B; Sanchez, M C; Santucci, G; Schmitz, D; Scholberg, K; Seckel, D; Shaevitz, M; Shrock, R; Smy, M B; Soderberg, M; Sonzogni, A; Sousa, A B; Spitz, J; John, J M St; Stewart, J; Strait, J B; Sullivan, G; Svoboda, R; Szelc, A M; Tayloe, R; Thomson, M A; Toups, M; Vacheret, A; Vagins, M; Van de Water, R G; Vogelaar, R B; Weber, M; Weng, W; Wetstein, M; White, C; White, B R; Whitehead, L; Whittington, D W; Wilking, M J; Wilson, R J; Wilson, P; Winklehner, D; Winn, D R; Worcester, E; Yang, L; Yeh, M; Yokley, Z W; Yoo, J; Yu, B; Yu, J; Zhang, C


    The US neutrino community gathered at the Workshop on the Intermediate Neutrino Program (WINP) at Brookhaven National Laboratory February 4-6, 2015 to explore opportunities in neutrino physics over the next five to ten years. Scientists from particle, astroparticle and nuclear physics participated in the workshop. The workshop examined promising opportunities for neutrino physics in the intermediate term, including possible new small to mid-scale experiments, US contributions to large experiments, upgrades to existing experiments, R&D plans and theory. The workshop was organized into two sets of parallel working group sessions, divided by physics topics and technology. Physics working groups covered topics on Sterile Neutrinos, Neutrino Mixing, Neutrino Interactions, Neutrino Properties and Astrophysical Neutrinos. Technology sessions were organized into Theory, Short-Baseline Accelerator Neutrinos, Reactor Neutrinos, Detector R&D and Source, Cyclotron and Meson Decay at Rest sessions.This report summ...

  18. The Intermediate Neutrino Program

    Energy Technology Data Exchange (ETDEWEB)

    Adams, C.; et al.


    The US neutrino community gathered at the Workshop on the Intermediate Neutrino Program (WINP) at Brookhaven National Laboratory February 4-6, 2015 to explore opportunities in neutrino physics over the next five to ten years. Scientists from particle, astroparticle and nuclear physics participated in the workshop. The workshop examined promising opportunities for neutrino physics in the intermediate term, including possible new small to mid-scale experiments, US contributions to large experiments, upgrades to existing experiments, R&D plans and theory. The workshop was organized into two sets of parallel working group sessions, divided by physics topics and technology. Physics working groups covered topics on Sterile Neutrinos, Neutrino Mixing, Neutrino Interactions, Neutrino Properties and Astrophysical Neutrinos. Technology sessions were organized into Theory, Short-Baseline Accelerator Neutrinos, Reactor Neutrinos, Detector R&D and Source, Cyclotron and Meson Decay at Rest sessions.This report summarizes discussion and conclusions from the workshop.

  19. Cation-{pi}-interaction promoted aggregation of aromatic molecules and energy transfer within Y zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, K.J.; Sunoj, R.B.; Chandrasekhar, J.; Ramamurthy, V.


    Photophysical studies of naphthalene confirm that aromatic molecules tend to aggregate within cation exchanged Y zeolites. Ground-state aggregation is traced to the presence of cation-aromatic {pi}-interaction. Solvents that can coordinate to the cation turn off the cation-aromatic interaction, and consequently aggregation does not occur in zeolites that are impregnated with the above solvents. The solvent that exhibits a maximum in such an effect is water. MP2 calculations on cation-benzene dimer indicate that cation-{pi}-interaction results in stabilization of the {pi}-stacked benzene dimer. Results of MP2 calculations are consistent with the formation of ground-state {pi}-stacked aggregates of naphthalene molecules within Y zeolites.

  20. Photodissociation of Cerium Oxide Nanocluster Cations. (United States)

    Akin, S T; Ard, S G; Dye, B E; Schaefer, H F; Duncan, M A


    Cerium oxide cluster cations, CexOy(+), are produced via laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. The mass spectrum displays a strongly preferred oxide stoichiometry for each cluster with a specific number of metal atoms x, with x ≤ y. Specifically, the most prominent clusters correspond to the formula CeO(CeO2)n(+). The cluster cations are mass selected and photodissociated with a Nd:YAG laser at either 532 or 355 nm. The prominent clusters dissociate to produce smaller species also having a similar CeO(CeO2)n(+) formula, always with apparent leaving groups of (CeO2). The production of CeO(CeO2)n(+) from the dissociation of many cluster sizes establishes the relative stability of these clusters. Furthermore, the consistent loss of neutral CeO2 shows that the smallest neutral clusters adopt the same oxidation state (IV) as the most common form of bulk cerium oxide. Clusters with higher oxygen content than the CeO(CeO2)n(+) masses are present with much lower abundance. These species dissociate by the loss of O2, leaving surviving clusters with the CeO(CeO2)n(+) formula. Density functional theory calculations on these clusters suggest structures composed of stable CeO(CeO2)n(+) cores with excess oxygen bound to the surface as a superoxide unit (O2(-)).

  1. FT-IR and 1H NMR studies of the state of solubilized water in water-in-oil microemulsions stabilized by mixtures of single- and double-tailed cationic surfactants. (United States)

    Bumajdad, Ali; Madkour, Metwally; Shaaban, Ehab; El Seoud, Omar A


    The structure of solubilized water in water-in-n-heptane aggregates stabilized by mixtures of single- and double-tail quaternary ammonium surfactants, namely didodecyldimethylammonium chloride/dodecyltrimethylammonium chloride (DDAC/DTAC) or didodecyldimethylammonium bromide/dodecyltrimethylammonium bromide (DDAB/DTAB) was studied by two noninvasive techniques, (1)H NMR and FT-IR. In the former, the chemical shift data, δ(obs), were used to calculate the so-called deuterium/protium fractionation factor, φ(M), of the aggregate-solubilized water and were found to be unity. In the FT-IR study, upon increasing water/surfactant molar ratio, W, the frequency, ν(OD), of the HOD species decreases, while its full width at half height and its area increase. The results obtained from both techniques indicate that the water appears to be present as a single nano-phase and the structure varies continuously as a result of increasing W. In addition, the effect of changing the counter-ion (Br(-) or Cl(-)) on (1)H NMR and FT-IR results was investigated. In spite of the known difference in the dissociation of these counter-ions from micellar aggregates, this was found not to affect the state of solubilized water. This report gives further insight into the contradictory scientific debates on the structure of water in the polar nano-cores of microemulsions.

  2. Local atomic structure in cubic stabilized zirconia

    Energy Technology Data Exchange (ETDEWEB)

    Villella, P.; Conradson, S. D.; Espinosa-Faller, F. J.; Foltyn, S. R.; Sickafus, K. E.; Valdez, J. A.; Degueldre, C. A.


    X-ray-absorption fine structure measurements have been used to elucidate the local atomic structure of quaternary Zr, Y, Er, Ce/U cubic stabilized zirconia. These compounds display more complicated local environments than those reported for simpler binary systems. While the shortest cation-O distances are similar to those found in the binary cubic stabilized compounds, responding to the different sizes of the cations, we have identified large distortions in the first-shell oxygen distribution involving long, 2.8--3.2 {angstrom} cation-O distances that are similar to those found in the amorphous phase of zirconium. The cation-cation distributions are also found to be quite complicated (non-Gaussian) and element specific. The U-near neighbor distances are expanded relative to the Ce ions for which it substitutes, consistent with the larger size of the actinide, and the U-cation distribution is also more complicated. In terms of the effects of this substitution on the other cation sites, the local environment around Y is altered while the Zr and Er local environments remain unchanged. These results point out the importance of collective and correlated interactions between the different pairs of cations and the host lattice that are mediated by the local strain fields generated by the different cations. The presence of pair-specific couplings has not been commonly included in previous analyses and may have implications for the stabilization mechanisms of cubic zirconia.

  3. Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process. (United States)

    Reshetnikov, Roman V; Sponer, Jiri; Rassokhina, Olga I; Kopylov, Alexei M; Tsvetkov, Philipp O; Makarov, Alexander A; Golovin, Andrey V


    A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange.

  4. Research progress in cation-π interactions

    Institute of Scientific and Technical Information of China (English)


    Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen bonding,electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper,we present an overview of the typical cation-π interactions in biological systems,the experimental and theoretical investigations on cation-π interactions,as well as the research results on cation-π interactions in our group.

  5. Research progress in cation-π interactions

    Institute of Scientific and Technical Information of China (English)

    CHENG JiaGao; LUO XiaoMin; YAN XiuHua; LI Zhong; TANG Yun; JIANG HuaLiang; ZHU WeiLiang


    Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system, which has been viewed as a new kind of binding force, as being compared with the classical interac-tions (e.g. hydrogen bonding, electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper, we present an overview of the typi-cal cation-π interactions in biological systems, the experimental and theoretical investigations on cation-π interactions, as well as the research results on cation-π interactions in our group.

  6. Manufacture of GdBa2Cu3O7−x Superconducting Thin Films Using High-Thermal-Stability Precursors Playing the Role of Intermediate-Phase Grain-Growth Inhibitors

    DEFF Research Database (Denmark)

    Tang, Xiao; He, Dong; Yue, Zhao;


    We have developed a fluorine-free metal–organic decomposition method using acrylic acid as the solvent for the synthesis of GdBCO superconducting thin films. Commonly used propionic acid was also used to make a comparison with acrylic acid. Acrylic acid was found to be polymerized during drying......, resulting in high thermal stability of the precursor solution. Due to the elevated decomposition temperature of the organic compounds in the acrylic-acid-based precursor, the formation of intermediate phases such as CuO was found delayed; therefore, the grain growth and phase segregation were suppressed....... The superior quality of pyrolyzed films induced by the use of polymerizable acrylic acid is reflected in the Jcof the GdBCO films, which achieved 1.2MA/cm2....

  7. Carbocation Stability in H-ZSM5 at High Temperature

    Energy Technology Data Exchange (ETDEWEB)

    Ferguson, Glen A. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Cheng, Lei [Argonne National Lab. (ANL), Argonne, IL (United States); Bu, Lintao [National Renewable Energy Lab. (NREL), Golden, CO (United States); Kim, Seonah [National Renewable Energy Lab. (NREL), Golden, CO (United States); Robichaud, David J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Nimlos, Mark R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Curtiss, Larry A. [Argonne National Lab. (ANL), Argonne, IL (United States); Beckham, Gregg T. [National Renewable Energy Lab. (NREL), Golden, CO (United States)


    Zeolites are common catalysts for multiple industrial applications, including alcohol dehydration to produce olefins, and given their commercial importance, reaction mechanisms in zeolites have long been proposed and studied. Some proposed reaction mechanisms for alcohol dehydration exhibit noncyclic carbocation intermediates or transition states that resemble carbocations, and several previous studies suggest that the tert-butyl cation is the only noncyclic cation more stable than the corresponding chemisorbed species with the hydrocarbon bound to the framework oxygen (i.e., an alkoxide). To determine if carbocations can exist at high temperatures in zeolites, where these catalysts are finding new applications for biomass vapor-phase upgrading (~500 °C), the stability of carbocations and the corresponding alkoxides were calculated with two ONIOM embedding methods (M06-2X/6-311G(d,p):M06-2X/3-21G) and (PBE-D3/6-311G(d,p):PBE-D3/3-21G) and plane-wave density functional theory (DFT) using the PBE functional corrected with entropic and Tkatchenko–Scheffler van der Waals corrections. Additionally, the embedding methods tested are unreliable at finding minima for primary carbocations, and only secondary or higher carbocations can be described with embedding methods consistent with the periodic DFT results. The relative energy between the carbocations and alkoxides differs significantly between the embedding and the periodic DFT methods. The difference is between ~0.23 and 14.30 kcal/mol depending on the molecule, the model, and the functional chosen for the embedding method. At high temperatures, the pw-DFT calculations predict that the allyl, isopropyl, and sec-butyl cations exhibit negligible populations while acetyl and tert-butyl cations exhibit significant populations (>10%). Furthermore, the periodic DFT results indicate that mechanisms including secondary and tertiary carbocations intermediates or carbocations stabilized by adjacent oxygen or double bonds are

  8. Crystal Defects and Cation Redistribution Study on Nanocrystalline Cobalt-Ferri-Chromites by Positron Annihilation Spectroscopy

    Directory of Open Access Journals (Sweden)

    Kunal B. Modi


    Full Text Available Positron lifetime and Doppler broadening measurements were carried out on nanocrystalline (grain size ~60–65 nm samples of the Cr3+-substituted cobalt ferrite system with general chemical formula CoCrxFe2−xO4 (x=0.0−2.0 synthesized by the coprecipitation technique. The results indicated selective trapping of positrons in large vacancy clusters initially at the tetrahedral (A- sites and then with Cr3+-substitution up to concentration (x=0.7, at the octahedral (B- sites. The results are consistent with the cation distribution determined from X-ray diffraction line intensity calculations, which indicated partial inversion of the inverse spinel ferrite, subsequent stabilization over a range of substitution (x=0.7 to 1.7, and finally the full inversion to the normal spinel chromite (CoCr2O4, x=2.0. In the intermediate range of substitution, lattice contraction prevented a fraction of Co2+ ions released from the (B- sites from entering the tetrahedral sites, and these vacancies at the (A- sites trapped positrons. Although the samples were composed of nanocrystalline grains, only an insignificant fraction of positrons were diffused and annihilated at the grain surfaces, since the grain sizes and the thermal diffusion length of positrons nearly overlapped.

  9. An efficient algorithm for finding the minimum energy path for cation migration in ionic materials (United States)

    Rong, Ziqin; Kitchaev, Daniil; Canepa, Pieremanuele; Huang, Wenxuan; Ceder, Gerbrand


    The Nudged Elastic Band (NEB) is an established method for finding minimum-energy paths and energy barriers of ion migration in materials, but has been hampered in its general application by its significant computational expense when coupled with density functional theory (DFT) calculations. Typically, an NEB calculation is initialized from a linear interpolation of successive intermediate structures (also known as images) between known initial and final states. However, the linear interpolation introduces two problems: (1) slow convergence of the calculation, particularly in cases where the final path exhibits notable curvature; (2) divergence of the NEB calculations if any intermediate image comes too close to a non-diffusing species, causing instabilities in the ensuing calculation. In this work, we propose a new scheme to accelerate NEB calculations through an improved path initialization and associated energy estimation workflow. We demonstrate that for cation migration in an ionic framework, initializing the diffusion path as the minimum energy path through a static potential built upon the DFT charge density reproduces the true NEB path within a 0.2 Å deviation and yields up to a 25% improvement in typical NEB runtimes. Furthermore, we find that the locally relaxed energy barrier derived from this initialization yields a good approximation of the NEB barrier, with errors within 20 meV of the true NEB value, while reducing computational expense by up to a factor of 5. Finally, and of critical importance for the automation of migration path calculations in high-throughput studies, we find that the new approach significantly enhances the stability of the calculation by avoiding unphysical image initialization. Our algorithm promises to enable efficient calculations of diffusion pathways, resolving a long-standing obstacle to the computational screening of intercalation compounds for Li-ion and multivalent batteries.

  10. An efficient algorithm for finding the minimum energy path for cation migration in ionic materials. (United States)

    Rong, Ziqin; Kitchaev, Daniil; Canepa, Pieremanuele; Huang, Wenxuan; Ceder, Gerbrand


    The Nudged Elastic Band (NEB) is an established method for finding minimum-energy paths and energy barriers of ion migration in materials, but has been hampered in its general application by its significant computational expense when coupled with density functional theory (DFT) calculations. Typically, an NEB calculation is initialized from a linear interpolation of successive intermediate structures (also known as images) between known initial and final states. However, the linear interpolation introduces two problems: (1) slow convergence of the calculation, particularly in cases where the final path exhibits notable curvature; (2) divergence of the NEB calculations if any intermediate image comes too close to a non-diffusing species, causing instabilities in the ensuing calculation. In this work, we propose a new scheme to accelerate NEB calculations through an improved path initialization and associated energy estimation workflow. We demonstrate that for cation migration in an ionic framework, initializing the diffusion path as the minimum energy path through a static potential built upon the DFT charge density reproduces the true NEB path within a 0.2 Å deviation and yields up to a 25% improvement in typical NEB runtimes. Furthermore, we find that the locally relaxed energy barrier derived from this initialization yields a good approximation of the NEB barrier, with errors within 20 meV of the true NEB value, while reducing computational expense by up to a factor of 5. Finally, and of critical importance for the automation of migration path calculations in high-throughput studies, we find that the new approach significantly enhances the stability of the calculation by avoiding unphysical image initialization. Our algorithm promises to enable efficient calculations of diffusion pathways, resolving a long-standing obstacle to the computational screening of intercalation compounds for Li-ion and multivalent batteries.

  11. Stabilization of reactive species by supramolecular encapsulation. (United States)

    Galan, Albano; Ballester, Pablo


    Molecular containers have attracted the interest of supramolecular chemists since the early beginnings of the field. Cavitands' inner cavities were quickly exploited by Cram and Warmuth to construct covalent containers able to stabilize and assist the characterization of short-lived reactive species such as cyclobutadiene or o-benzyne. Since then, more complex molecular architectures have been prepared able to store and isolate a myriad of fleeting species (i.e. organometallic compounds, cationic species, radical initiators…). In this review we cover selected examples of the stabilization of reactive species by encapsulation in molecular containers from the first reports of covalent containers described by Cram et al. to the most recent examples of containers with self-assembled structure (metal coordination cages and hydrogen bonded capsules). Finally, we briefly review examples reported by Rebek et al. in which elusive reaction intermediates could be detected in the inner cavities of self-folding resorcin[4]arene cavitands by the formation of covalent host-guest complexes. The utilization of encapsulated reactive species in catalysis or synthesis is not covered.

  12. Blackbody-induced radiative dissociation of cationic SF 6 clusters

    DEFF Research Database (Denmark)

    Toker, Jonathan; Rahinov, I.; Schwalm, D.;


    The stability of cationic SF5+(SF6)n−1 clusters was investigated by measuring their blackbody-induced radiative dissociation (BIRD) rates. The clusters were produced in a supersonic expansion ion source and stored in an electrostatic ion-beam trap at room temperature, where their abundances...... and lifetimes were measured. Using the “master equation” approach, relative binding energies of an SF6 unit in the clusters could be extracted from the storage-time dependence of the survival probabilities. The results allow for a deeper insight into the effect of a localized charge on the structure...... and stability of SF6-based clusters....

  13. Electrophilic Pt(II) complexes: precision instruments for the initiation of transformations mediated by the cation-olefin reaction. (United States)

    Felix, Ryan J; Munro-Leighton, Colleen; Gagné, Michel R


    A discontinuity exists between the importance of the cation-olefin reaction as the principal C-C bond forming reaction in terpene biosynthesis and the synthetic tools for mimicking this reaction under catalyst control; that is, having the product identity, stereochemistry, and functionality under the control of a catalyst. The main reason for this deficiency is that the cation-olefin reaction starts with a reactive intermediate (a carbocation) that reacts exothermically with an alkene to reform the reactive intermediate; not to mention that reactive intermediates can also react in nonproductive fashions. In this Account, we detail our efforts to realize catalyst control over this most fundamental of reactions and thereby access steroid like compounds. Our story is organized around our progress in each component of the cascade reaction: the metal controlled electrophilic initiation, the propagation and termination of the cyclization (the cyclase phase), and the turnover deplatinating events. Electrophilic Pt(II) complexes efficiently initiate the cation-olefin reaction by first coordinating to the alkene with selection rules that favor less substituted alkenes over more substituted alkenes. In complex substrates with multiple alkenes, this preference ensures that the least substituted alkene is always the better ligand for the Pt(II) initiator, and consequently the site at which all electrophilic chemistry is initiated. This control element is invariant. With a suitably electron deficient ligand set, the catalyst then activates the coordinated alkene to intramolecular addition by a second alkene, which initiates the cation-olefin reaction cascade and generates an organometallic Pt(II)-alkyl. Deplatination by a range of mechanisms (β-H elimination, single electron oxidation, two-electron oxidation, etc.) provides an additional level of control that ultimately enables A-ring functionalizations that are orthogonal to the cyclase cascade. We particularly focus on

  14. Heavy metal cations permeate the TRPV6 epithelial cation channel. (United States)

    Kovacs, Gergely; Danko, Tamas; Bergeron, Marc J; Balazs, Bernadett; Suzuki, Yoshiro; Zsembery, Akos; Hediger, Matthias A


    TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications.

  15. The adjuvant mechanism of cationic dimethyldioctadecylammonium liposomes

    DEFF Research Database (Denmark)

    Korsholm, Karen Smith; Agger, Else Marie; Foged, Camilla;


    Cationic liposomes are being used increasingly as efficient adjuvants for subunit vaccines but their precise mechanism of action is still unknown. Here, we investigated the adjuvant mechanism of cationic liposomes based on the synthetic amphiphile dimethyldioctadecylammonium (DDA). The liposomes ...

  16. Tripodal Receptors for Cation and Anion Sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman,; Verboom, Willem; Reinhoudt, David N.


    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  17. Influence of water on anharmonicity, stability, and vibrational energy distribution of hydrogen-bonded adducts in atmospheric reactions: case study of the OH + isoprene reaction intermediate using ab initio molecular dynamics. (United States)

    Dietrick, Scott M; Pacheco, Alexander B; Phatak, Prasad; Stevens, Philip S; Iyengar, Srinivasan S


    The effect of water on the stability and vibrational states of a hydroxy-isoprene adduct is probed through the introduction of 1-15 water molecules. It is found that when a static nuclear harmonic approximation is invoked there is a substantial red-shift of the alcohol O-H stretch (of the order of 800 cm(-1)) as a result of introduction of water. When potential energy surface sampling and associated anharmonicities are introduced through finite temperature ab initio dynamics, this hydroxy-isoprene OH stretch strongly couples with all the water vibrational modes as well as the hydroxy-isoprene OH bend modes. A new computational technique is introduced to probe the coupling between these modes. The method involves a two-dimensional, time-frequency analysis of the finite temperature vibrational properties. Such an analysis not only provides information about the modes that are coupled as a result of finite-temperature analysis, but also the temporal evolution of such coupling.

  18. Theoretical study of the influence of cation vacancies on the catalytic properties of vanadium antimonate

    Energy Technology Data Exchange (ETDEWEB)

    Messina, S. [Laboratorio de Procesos Cataliticos, Departamento de Ingenieria Quimica, FIUBA, Pabellon de Industrias, Ciudad Universitaria, (1428) Capital Federal (Argentina); Juan, A. [Departamento de Fisica, UNS, Av. Alem 1253, (8000) Bahia Blanca (Argentina)], E-mail:; Larrondo, S.; Irigoyen, B.; Amadeo, N. [Laboratorio de Procesos Cataliticos, Departamento de Ingenieria Quimica, FIUBA, Pabellon de Industrias, Ciudad Universitaria, (1428) Capital Federal (Argentina)


    We have theoretically studied the influence of antimony and vanadium cation vacancies in the electronic structure and reactivity of vanadium antimonate, using molecular orbital methods. From the analysis of the electronic properties of the VSbO{sub 4} crystal structure, we can infer that both antimony and vanadium vacancies increase the oxidation state of closer V cations. This would indicate that, in the rutile-type VSbO{sub 4} phase the Sb and V cations defects stabilize the V in a higher oxidation state (V{sup 4+}). Calculations of the adsorption energy for different toluene adsorption geometries on the VSbO{sub 4}(1 1 0) surface have also been performed. The oxidation state of Sb, V and O atoms and the overlap population of metal-oxygen bonds have been evaluated. Our results indicate that the cation defects influence in the toluene adsorption reactions is slight. We have computed different alternatives for the reoxidation of the VSbO{sub 4}(1 1 0) surface active sites which were reduced during the oxygenated products formation. These calculations indicate that the V cations in higher oxidation state (V{sup 4+}) are the species, which preferentially incorporate lattice oxygen to the reduced Sb cations. Thus, the cation defects would stabilize the V{sup 4+} species in the VSbO{sub 4} structure, determining its ability to provide lattice oxygen as a reactant.

  19. Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

    KAUST Repository

    Dey, Raju


    Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

  20. Cationic Tungsten(VI Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

    Directory of Open Access Journals (Sweden)

    Dey Raju


    Full Text Available Tungsten-hexa-methyl readily reacts with B(C6F53 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

  1. Dee-Mack Intermediate School (United States)

    Northwest Evaluation Association, 2012


    Frank Reliford, the Principal at Dee-Mack Intermediate since 2005, is familiar to almost every child in the community. 260 Students attend Reliford's school, and their status is a point of pride: Dee-Mack Intermediate is consistently one of the highest performing schools in the state. The change in student performance correlates to the…

  2. Welding. Performance Objectives. Intermediate Course. (United States)

    Vincent, Kenneth

    Several intermediate performance objectives and corresponding criterion measures are listed for each of nine terminal objectives for an intermediate welding course. The materials were developed for a 36-week (3 hours daily) course designed to prepare the student for employment in the field of welding. Electric welding and specialized (TIG & MIG)…

  3. The role of the alkali and chalcogen atoms on the stability of the layered chalcogenide \\mathbf{{{A}_{2}}{{M}^{II}}M_{3}^{\\,IV}{{Q}_{8}}} (A  =  alkali-metal M  =  metal-cations Q  =  chalcogen) compounds: a density functional theory investigation within van der Waals corrections (United States)

    Besse, Rafael; Da Silva, Juarez L. F.


    There is a great interest to design two-dimensional (2D) chalcogenide materials, however, our atomistic understanding of the major physical parameters that drive the formation of 2D or three-dimensional (3D) chalcogenides is far from satisfactory, in particular, for complex quaternary systems. To address this problem, we selected a set of quaternary 2D and 3D chalcogenide compounds, namely, {{\\text{A}}2}\\text{ZnS}{{\\text{n}}3}{{\\text{Q}}8} (A  =  Li, K, Cs; Q  =  S, Se, Te), which were investigated by density functional theory calculations within van der Waals (vdW) corrections. Employing experimental crystal structures and well designed crystal modifications, we found that the average atomic radius of the alkali-metal, A, and chalcogen, Q, species play a crucial role in the stability of the 2D structures. For example, the 2D structures are energetically favored for smaller (R1.8~{\\mathring{\\text{A}}}) average atomic radius, while 3D structures are favored at intermediate average atomic radius. Those results are explained in terms of strain minimization and Coulomb repulsion of the anionic species in the structure framework. Furthermore, the equilibrium lattice parameters are in excellent agreement with experimental results. Thus, the present insights can help in the design of stable quartenary 2D chalcogenide compounds.

  4. Intermediate dosimetric quantities. (United States)

    Kellerer, A M; Hahn, K; Rossi, H H


    The transfer of energy from ionizing radiation to matter involves a series of steps. In wide ranges of their energy spectra photons and neutrons transfer energy to an irradiated medium almost exclusively by the production of charged particles which ionize and thereby produce electrons that can ionize in turn. The examination of these processes leads to a series of intermediate quantities. One of these is kerma, which has long been employed as a measure of the energy imparted in the first of the interactions. It depends only on the fluence of uncharged particles and is therefore--unlike absorbed dose and electron fluence--insensitive to local differences of receptor geometry and composition. An analogous quantity for charged-particle fields, cema (converted energy per unit mass), is defined, which quantifies the energy imparted in terms of the interactions of charged particles, disregarding energy dissipation by secondary electrons. Cema can be expressed as an integral over the fluence of ions times their stopping power. However, complications arise when the charged particles are electrons, and when their fluence cannot be separated from that of the secondaries. The resulting difficulty can be circumvented by the definition of reduced cema. This quantity corresponds largely to the concept employed in the cavity theory of Spencer and Attix. In reduced cema not all secondary electrons but all electrons below a chosen cutoff energy, delta, are considered to be absorbed locally. When the cutoff energy is reduced, cema approaches absorbed dose and thereby becomes sensitive to highly local differences in geometry or composition. With larger values of delta, reduced cema is a useful parameter to specify the dose-generating potential of a charged-particle field 'free in air' or in vacuo. It is nearly equal to the mean absorbed dose in a sphere with radius equal to the range of electrons of energy delta. Reduced cema is a function of the fluence at the specified location at

  5. Stabilizing brokerage. (United States)

    Stovel, Katherine; Golub, Benjamin; Milgrom, Eva M Meyersson


    A variety of social and economic arrangements exist to facilitate the exchange of goods, services, and information over gaps in social structure. Each of these arrangements bears some relationship to the idea of brokerage, but this brokerage is rarely like the pure and formal economic intermediation seen in some modern markets. Indeed, for reasons illuminated by existing sociological and economic models, brokerage is a fragile relationship. In this paper, we review the causes of instability in brokerage and identify three social mechanisms that can stabilize fragile brokerage relationships: social isolation, broker capture, and organizational grafting. Each of these mechanisms rests on the emergence or existence of supporting institutions. We suggest that organizational grafting may be the most stable and effective resolution to the tensions inherent in brokerage, but it is also the most institutionally demanding.

  6. Solidification cracking in austenitic stainless steel welds

    Indian Academy of Sciences (India)

    V Shankar; T P S Gill; S L Mannan; S Sundaresan


    Solidification cracking is a significant problem during the welding of austenitic stainless steels, particularly in fully austenitic and stabilized compositions. Hot cracking in stainless steel welds is caused by low-melting eutectics containing impurities such as S, P and alloy elements such as Ti, Nb. The WRC-92 diagram can be used as a general guide to maintain a desirable solidification mode during welding. Nitrogen has complex effects on weld-metal microstructure and cracking. In stabilized stainless steels, Ti and Nb react with S, N and C to form low-melting eutectics. Nitrogen picked up during welding significantly enhances cracking, which is reduced by minimizing the ratio of Ti or Nb to that of C and N present. The metallurgical propensity to solidification cracking is determined by elemental segregation, which manifests itself as a brittleness temperature range or BTR, that can be determined using the varestraint test. Total crack length (TCL), used extensively in hot cracking assessment, exhibits greater variability due to extraneous factors as compared to BTR. In austenitic stainless steels, segregation plays an overwhelming role in determining cracking susceptibility.

  7. High DNA-Binding Affinity and Gene-Transfection Efficacy of Bioreducible Cationic Nanomicelles with a Fluorinated Core. (United States)

    Wang, Long-Hai; Wu, De-Cheng; Xu, Hang-Xun; You, Ye-Zi


    During the last two decades, cationic polymers have become one of the most promising synthetic vectors for gene transfection. However, the weak interactions formed between DNA and cationic polymers result in low transfection efficacy. Furthermore, the polyplexes formed between cationic polymers and DNA generally exhibit poor stability and toxicity because of the large excess of cationic polymer typically required for complete DNA condensation. Herein, we report the preparation of a novel class of bioreducible cationic nanomicelles by the use of disulfide bonds to connect the cationic shell to the fluorocarbon core. These bioreducible nanomicelles form strong interactions with DNA and completely condense DNA at an N/P ratio of 1. The resulting nanomicelle/DNA polyplexes exhibited high biocompatibility and performed very effectively as a gene-delivery system.

  8. Measurement of antioxidant activity with trifluoperazine dihydrochloride radical cation

    Directory of Open Access Journals (Sweden)

    M.N. Asghar


    Full Text Available A novel, rapid and cost-effective trifluoperazine dihydrochloride (TFPH decolorization assay is described for the screening of antioxidant activity. A chromogenic reaction between TFPH and potassium persulfate at low pH produces an orange-red radical cation with maximum absorption at 502 nm in its first-order derivative spectrum. TFPH was dissolved in distilled water to give a 100 mM solution. The TFPH radical cation solution was made by reacting 0.5 mL of the solution with K2S2O8 (final concentration: 0.1 mM and diluting to 100 mL with 4 M H2SO4 solution. A linear inhibition of color production was observed with linearly increasing amounts of antioxidants, with correlation coefficients (R² ranging from 0.999 to 0.983. The antioxidant capacity of standard solutions of an antioxidant was evaluated by comparing with the inhibition curve using Trolox as the standard. Comparison of antioxidant capacity determined with this newly developed TFPH assay and with the well-known 2,2'-azinobis-[3-ethylbenzthiazoline-6-sulfonic acid] (ABTS-persulfate decolorization assay indicated the efficacy and sensitivity of the procedure. The proposed assay is less expensive (costs about US$4 per 100 assays and requires only 20 min for preparation of radical cation solution in comparison with ABTS assay, in which almost 12-16 h are required for preparation of a stable ABTS radical cation solution. The present assay has the advantage over ABTS assay that it can be used to measure the antioxidant activity of the samples, which are naturally found at a pH as low as 1, because the radical cation itself has been stabilized at low pH.

  9. Mechanical Properties of Intermediate Filament Proteins. (United States)

    Charrier, Elisabeth E; Janmey, Paul A


    Purified intermediate filament (IF) proteins can be reassembled in vitro to produce polymers closely resembling those found in cells, and these filaments form viscoelastic gels. The cross-links holding IFs together in the network include specific bonds between polypeptides extending from the filament surface and ionic interactions mediated by divalent cations. IF networks exhibit striking nonlinear elasticity with stiffness, as quantified by shear modulus, increasing an order of magnitude as the networks are deformed to large strains resembling those that soft tissues undergo in vivo. Individual IFs can be stretched to more than two or three times their resting length without breaking. At least 10 different rheometric methods have been used to quantify the viscoelasticity of IF networks over a wide range of timescales and strain magnitudes. The mechanical roles of different classes of cytoplasmic IFs on mesenchymal and epithelial cells in culture have also been studied by an even wider range of microrheological methods. These studies have documented the effects on cell mechanics when IFs are genetically or pharmacologically disrupted or when normal or mutant IF proteins are exogenously expressed in cells. Consistent with in vitro rheology, the mechanical role of IFs is more apparent as cells are subjected to larger and more frequent deformations.

  10. Novel cationic polyelectrolyte coatings for capillary electrophoresis. (United States)

    Duša, Filip; Witos, Joanna; Karjalainen, Erno; Viitala, Tapani; Tenhu, Heikki; Wiedmer, Susanne K


    The use of bare fused silica capillary in CE can sometimes be inconvenient due to undesirable effects including adsorption of sample or instability of the EOF. This can often be avoided by coating the inner surface of the capillary. In this work, we present and characterize two novel polyelectrolyte coatings (PECs) poly(2-(methacryloyloxy)ethyl trimethylammonium iodide) (PMOTAI) and poly(3-methyl-1-(4-vinylbenzyl)-imidazolium chloride) (PIL-1) for CE. The coated capillaries were studied using a series of aqueous buffers of varying pH, ionic strength, and composition. Our results show that the investigated polyelectrolytes are usable as semi-permanent (physically adsorbed) coatings with at least five runs stability before a short coating regeneration is necessary. Both PECs showed a considerably decreased stability at pH 11.0. The EOF was higher using Good's buffers than with sodium phosphate buffer at the same pH and ionic strength. The thickness of the PEC layers studied by quartz crystal microbalance was 0.83 and 0.52 nm for PMOTAI and PIL-1, respectively. The hydrophobicity of the PEC layers was determined by analysis of a homologous series of alkyl benzoates and expressed as the distribution constants. Our result demonstrates that both PECs had comparable hydrophobicity, which enabled separation of compounds with log Po/w > 2. The ability to separate cationic drugs was shown with β-blockers, compounds often misused in doping. Both coatings were also able to separate hydrolysis products of the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-ene acetate at highly acidic conditions, where bare fused silica capillaries failed to accomplish the separation.

  11. On the feasibility of designing hyperalkali cations using superalkali clusters as ligands (United States)

    Sun, Wei-Ming; Li, Xiang-Hui; Li, Ying; Liu, Jia-Yuan; Wu, Di; Li, Chun-Yan; Ni, Bi-Lian; Li, Zhi-Ru


    The possibility of using superalkali clusters instead of alkali atoms as ligands to design a class of cationic compounds, referred to as hyperalkali cations, has been examined by using gradient-corrected density functional theory. By taking typical superalkalis (FLi2, OLi3, and NLi4) as examples, a series of hyperalkali cations ML2+ [M = (super)halogen; L = superalkali] have been constructed and investigated. Calculational results show that all the superalkali moieties preserve their geometric and electronic integrity in these proposed cations. The stability of these studied cations is guaranteed by the strong ionic bonds between superalkali ligand and (super)halogen core, as well as their large highest occupied molecular orbital-lowest unoccupied molecular orbital gaps and positive dissociation energies. In particular, all these proposed cations possess lower vertical electron affinities (2.36-3.56 eV) than those of their corresponding cationic superalkali ligands, verifying their hyperalkali nature. We, therefore, hope that this study will provide an approach to obtain new species with excellent reducing capability by utilizing various superalkalis as building blocks.

  12. Direct observation of hexamethylbenzenium radical cations generated during zeolite methanol-to-olefin catalysis: an ESR study. (United States)

    Kim, Sun Jung; Jang, Hoi-Gu; Lee, Jun Kyu; Min, Hyung-Ki; Hong, Suk Bong; Seo, Gon


    The generation of hexamethylbenzenium radical cations as the key reaction intermediate in chabazite-type molecular sieve acids (i.e., H-SAPO-34 and H-SSZ-13) during the methanol-to-olefin process has been directly evidenced by ESR spectroscopy.

  13. Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Hanzhong, E-mail: [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Li, Li [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Chen, Hongxia; Zhao, Yue [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); School of Geology and Mining Engineering, Xinjiang University, Urumqi 830046 (China); Li, Xiyou [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Wang, Chuanyi, E-mail: [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China)


    Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe{sup 3+} > Al{sup 3+} > Cu{sup 2+} >> Ca{sup 2+} > K{sup +} > Na{sup +}, which is consistent with the binding energy of cation–π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation–π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na{sup +}-smectite and K{sup +}-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe{sup 3+}, Al{sup 3+}, and Cu{sup 2+} are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O{sub 2}{sup −}· , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation.

  14. Preparation and Photochemical Behavior of a Cationic Azobenzene Dye-Montmorillonite Intercalation Compound

    Institute of Scientific and Technical Information of China (English)


    Montmorillonite/cationic azobenzene dye(p-(δ-triethylammoniobutoxy)-p'-methyl-azobenzene bromide) intercalation compounds were prepared by the conventional ion exchange method. As compared with that of pure cationic azo-dye, the thermal stability of the intercalated dye was greatly enhanced, and the absorption band corresponding to azobenzene group in intercalated dye shifted towards longer wave length by 38 nm. This could be ascribed to the strong conjugation of cationic azo-dye supramolecular order structure(J cluster) confined in a nanoscale space of montmorillonite interlayer gallery. UV/vis spectra data show that the intercalated azo dye in the montmorillonite interlayer space exhibited reversible trans-to-cis photoisomerization and daylight cis-to-trans back reaction. FTIR indicates the successful intercalation of cationic azo-dye into the montmorillonite interlayer.

  15. Gulf of Maine intermediate water

    Energy Technology Data Exchange (ETDEWEB)

    Hopkins, T.S. (Brookhaven National Lab., Upton, NY); Garfield, N. III


    The thermohaline dynamics of the Gulf of Maine are analyzed from the two year, eight cruise, data set of Colton, Marak, Nickerson, and Stoddard (1968). Six water masses are described: the Maine Surface Water, Maine Intermediate Water, and the Maine Bottom Water as interior water masses; and the Scotian Shelf Water, the Slope Water, and the Georges Bank Water as exterior water masses. Particular attention is given to the formation and disposition of the Maine Intermediate Water. Salt balance, T-S volume, and T-S drift analyses are used to provide transport and mixing estimates for the year 1966. The Slope Water entered at depth through the Northeast Channel at a rate of 2600 km/sup 3//yr; while the Scotian Shelf Water entered the surface and intermediate layers, mostly during winter intrusions, at a rate of 5200 km/sup 3//yr. The surface and intermediate layers exported a total of 7900 km/sup 3//yr in a 3:5 ratio, respectively. The Maine Intermediate Water tends to collect over the Wilkinson Basin during the stratified season, to exit via the Great South Channel during early spring, and to exit via the Northeast Channel during spring and summer. Comparisons are made between the estimated winter heat loss of 280 Ly/d and the observed heat losses of 230 Ly/d (surface layers) and 360 Ly/d (surface and intermediate layers). A limit for the Scotian Shelf Water contribution is about -70 Ly/d. It is concluded that the Maine Intermediate Water is produced locally and that it is exported in significant quantities.

  16. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick


    Full Text Available In contrast to English, automatic hyphenation by computer of Afrikaans words is a problem that still needs to be addressed, since errors are still often encountered in printed text. An initial step in this task is the ability to automatically syllabify words. Since new words are created continuously by joining words, it is necessary to develop an “intelligent” technique for syllabification. As a first phase of the research, we consider only the orthographic information of words, and disregard both syntactic and morphological information. This approach allows us to use machine-learning techniques such as artificial neural networks and decision trees that are known for their pattern recognition abilities. Both these techniques are trained with isolated patterns consisting of input patterns and corresponding outputs (or targets that indicate whether the input pattern should be split at a certain position, or not. In the process of compiling a list of syllabified words from which to generate training data for the  syllabification problem, irregular patterns were identified. The same letter patterns are split differently in different words and complete words that are spelled identically are split differently due to meaning. We also identified irregularities in and between  the different dictionaries that we used. We examined the influence range of letters that are involved in irregularities. For example, for their in agter-ente and vaste-rente we have to consider three letters to the left of r to be certain where the hyphen should be inserted. The influence range of the k in verstek-waarde and kleinste-kwadrate is four to the left and three to the right. In an analysis of letter patterns in Afrikaans words we found that the letter e has the highest frequency overall (16,2% of all letters in the word list. The frequency of words starting with s is the highest, while the frequency of words ending with e is the highest. It is important to

  17. Anaerobic toxicity of cationic silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Gitipour, Alireza; Thiel, Stephen W. [Biomedical, Chemical, and Environmental Engineering, University of Cincinnati, Cincinnati, OH (United States); Scheckel, Kirk G. [USEPA, Office of Research and Development, Cincinnati, OH (United States); Tolaymat, Thabet, E-mail: [USEPA, Office of Research and Development, Cincinnati, OH (United States)


    The microbial toxicity of silver nanoparticles (AgNPs) stabilized with different capping agents was compared to that of Ag{sup +} under anaerobic conditions. Three AgNPs were investigated: (1) negatively charged citrate-coated AgNPs (citrate-AgNPs), (2) minimally charged polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) and (3) positively charged branched polyethyleneimine coated AgNPs (BPEI-AgNPs). The AgNPs investigated in this experiment were similar in size (10–15 nm), spherical in shape, but varied in surface charge which ranged from highly negative to highly positive. While, at AgNPs concentrations lower than 5 mg L{sup −1}, the anaerobic decomposition process was not influenced by the presence of the nanoparticles, there was an observed impact on the diversity of the microbial community. At elevated concentrations (100 mg L{sup −1} as silver), only the cationic BPEI-AgNPs demonstrated toxicity similar in magnitude to that of Ag{sup +}. Both citrate and PVP-AgNPs did not exhibit toxicity at the 100 mg L{sup −1} as measured by biogas evolution. These findings further indicate the varying modes of action for nanoparticle toxicity and represent one of the few studies that evaluate end-of-life management concerns with regards to the increasing use of nanomaterials in our everyday life. These findings also highlight some of the concerns with a one size fits all approach to the evaluation of environmental health and safety concerns associated with the use of nanoparticles. - Highlights: • At concentrations -1 the anaerobic decomposition process was not impacted. • An impact on the microbial community at concentrations -1 were observed. • At high concentrations (100 mg L{sup −1}), the cationic BPEI-AgNPs demonstrated toxicity. • Toxicity was demonstrated without the presence of oxidative dissolution of silver. • A one size fits all approach for the evaluation of NPs may not be accurate.

  18. Intermediate Temperature Solid Oxide Fuel Cell Development

    Energy Technology Data Exchange (ETDEWEB)

    S. Elangovan; Scott Barnett; Sossina Haile


    Solid oxide fuel cells (SOFCs) are high efficiency energy conversion devices. Present materials set, using yttria stabilized zirconia (YSZ) electrolyte, limit the cell operating temperatures to 800 C or higher. It has become increasingly evident however that lowering the operating temperature would provide a more expeditious route to commercialization. The advantages of intermediate temperature (600 to 800 C) operation are related to both economic and materials issues. Lower operating temperature allows the use of low cost materials for the balance of plant and limits degradation arising from materials interactions. When the SOFC operating temperature is in the range of 600 to 700 C, it is also possible to partially reform hydrocarbon fuels within the stack providing additional system cost savings by reducing the air preheat heat-exchanger and blower size. The promise of Sr and Mg doped lanthanum gallate (LSGM) electrolyte materials, based on their high ionic conductivity and oxygen transference number at the intermediate temperature is well recognized. The focus of the present project was two-fold: (a) Identify a cell fabrication technique to achieve the benefits of lanthanum gallate material, and (b) Investigate alternative cathode materials that demonstrate low cathode polarization losses at the intermediate temperature. A porous matrix supported, thin film cell configuration was fabricated. The electrode material precursor was infiltrated into the porous matrix and the counter electrode was screen printed. Both anode and cathode infiltration produced high performance cells. Comparison of the two approaches showed that an infiltrated cathode cells may have advantages in high fuel utilization operations. Two new cathode materials were evaluated. Northwestern University investigated LSGM-ceria composite cathode while Caltech evaluated Ba-Sr-Co-Fe (BSCF) based pervoskite cathode. Both cathode materials showed lower polarization losses at temperatures as low as 600

  19. Selective Facet Reactivity During Cation Exchange in Cadmium Sulfide Nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Sadtler, Bryce; Demchenko, Denis; Zheng, Haimei; Hughes, Steven; Merkle, Maxwell; Dahmen, Ulrich; Wang, Lin-Wang; Alivisatos, A. Paul


    The partial transformation of ionic nanocrystals through cation exchange has been used to synthesize nanocrystal heterostructures. We demonstrate that the selectivity for cation exchange to take place at different facets of the nanocrystal plays an important role in determining the resulting morphology of the binary heterostructure. In the case of copper I (Cu+) cation exchange in cadmium sulfide (CdS) nanorods, the reaction starts preferentially at the ends of the nanorods such that copper sulfide (Cu2S) grows inwards from either end. The resulting morphology is very different from the striped pattern obtained in our previous studies of silver I (Ag+) exchange in CdS nanorods where non-selective nucleation of silver sulfide (Ag2S) occurs. From interface formation energies calculated for several models of epitaxialconnections between CdS and Cu2S or Ag2S, we infer the relative stability of each interface during the nucleation and growth of Cu2S or Ag2S within the CdS nanorods. The epitaxial connections of Cu2S to the end facets of CdS nanorods minimize the formation energy, making these interfaces stable throughout the exchange reaction. However, as the two end facets of wurtzite CdS nanorods are crystallographically nonequivalent, asymmetric heterostructures can be produced.

  20. Naphthoxy Bounded Ferrocenium Salts as Cationic Photoinitiators for Epoxy Photopolymerization

    Directory of Open Access Journals (Sweden)

    Zh. Q. Li


    Full Text Available To improve the absorption and the bulk of arene ligands, two naphthoxy bounded ferrocenium salts as new cationic photoinitiators, (η6-α-naphthoxybenzene (η5-cyclopentadienyl iron hexafluorophosphate (NOFC-1 and (η6-β-naphthoxybenzene (η5-cyclopentadienyl iron hexafluorophosphate (NOFC-2, were synthesized, characterized, and studied. NOFC-1 and NOFC-2 were prepared by the reaction of nucleophilic substitution (SNAr with naphthol and chlorobenzene-cyclopentadienyliron salt. Their activity as cationic photoinitiators was studied using real-time infrared spectroscopy. The results obtained showed that NOFC-1 and NOFC-2 are capable of photoinitiating the cationic polymerization of epoxy monomer directly on irradiation with long-wavelength UV light (365 nm. Comparative studies also demonstrated that they exhibited better efficiency than cyclopentadienyl-Fe-cymene hexafluorophosphate (I-261. When NOFC-1 and NOFC-2 were used to efficiently initiate polymerization of epoxide, both rate of polymerization and final conversion increased using benzoyl peroxide (BPO as sensitizer. DSC studies showed that NOFC-1 and NOFC-2 photoinitiators in epoxides possess good thermal stability in the absence of light.

  1. Organophosphate Poisoning and Intermediate Syndrome

    Directory of Open Access Journals (Sweden)

    Mustafa Yilmaz


    Full Text Available Toxic effects that occur after acute organophosphate poisoning (OP can manifest three phases, namely, acute cholinergic crisis, intermediate syndrome and delayed-type polyneuropathy. Clinical signs and symptoms of organophosphate poisoning depend on the accumulation of acetylcholine at the nerve junction. Organophosphate poisoning causes three main clinical findings; acute cholinergic crisis consisting of muscarinic, nicotinic and central nervous system symptoms, intermediate syndrome with recurrence of cholinergic symptoms or muscle weakness without fasciculation 24-96 hours after poisoning and delayed-type polyneuropathy that can usually occur several days or weeks after acute exposure to organic phosphorus compounds. In this article, intermediate syndrome, which is a late complication, has been reviewed. [Archives Medical Review Journal 2016; 25(1.000: 70-83

  2. Effect of cation-π interactions and steric bulk on the catalytic action of oxidosqualene cyclase: a case study of Phe728 of β-amyrin synthase from Euphorbia tirucalli L. (United States)

    Ito, Ryousuke; Hashimoto, Ippei; Masukawa, Yukari; Hoshino, Tsutomu


    The function of the active-site residues of oxidosqualene cyclases (OSCs) has been presumed mainly in light of the product distribution; however, not much research has been performed into the enzymatic activity of mutated OSCs. β-Amyrin, which is widely found in the plant kingdom, is classified as an OSC; mutational studies on β-amyrin cyclase are very limited. Six site-specific mutations targeted at the Phe728 residue of Euphorbia tirucalli β-amyrin synthase (EtAS) were constructed to inspect the function of this aromatic residue. We developed a simple method to evaluate the in vivo enzymatic activity; the expression levels of EtASs and the quantities of the cyclic triterpenes produced were determined by use of western blot and GC analyses, respectively. Measurement of the relative in vivo activity of the mutants versus that of the wild-type enzyme showed that the Ala, Met, His, and Trp variants had significantly decreased activity, but that the Tyr mutant had a high activity, which was nearly the same as that of the wild-type enzyme. In contrast to Tyr, Ala and Met possess no π-electrons; thus, the role of Phe728 is to stabilize the cationic intermediates, resulting in facilitation of the ring-expansion processes, especially by stabilizing the secondary cations. The decreased activity of the Trp mutant is ascribed to the introduction of a large steric bulk, leading to looser binding of oxidosqualene in the Trp variant. The His mutant afforded germanicol as the main product, indicating that the Phe residue is located near the D/E-ring-formation site. Changes in the steric bulk gave some cationic intermediates, resulting in the formation of 13 cyclic triterpenes, including an unnatural triterpene, (17E)-dammara-17(20),24-dien-3β-ol, and isoursenol, which has rarely been found in nature. In this study, we provide the first experimental evidence that cation-π interactions play a key role in the catalytic action of OSCs.

  3. Keto-Enol Thermodynamics of Breslow Intermediates. (United States)

    Paul, Mathias; Breugst, Martin; Neudörfl, Jörg-Martin; Sunoj, Raghavan B; Berkessel, Albrecht


    Breslow intermediates, first postulated in 1958, are pivotal intermediates in carbene-catalyzed umpolung. Attempts to isolate and characterize these fleeting amino enol species first met with success in 2012 when we found that saturated bis-Dipp/Mes imidazolidinylidenes readily form isolable, though reactive diamino enols with aldehydes and enals. In contrast, triazolylidenes, upon stoichiometric reaction with aldehydes, gave exclusively the keto tautomer, and no isolable enol. Herein, we present the synthesis of the "missing" keto tautomers of imidazolidinylidene-derived diamino enols, and computational thermodynamic data for 15 enol-ketone pairs derived from various carbenes/aldehydes. Electron-withdrawing substituents on the aldehyde favor enol formation, the same holds for N,N'-Dipp [2,6-di(2-propyl)phenyl] and N,N'-Mes [2,4,6-trimethylphenyl] substitution on the carbene component. The latter effect rests on stabilization of the diamino enol tautomer by Dipp substitution, and could be attributed to dispersive interaction of the 2-propyl groups with the enol moiety. For three enol-ketone pairs, equilibration of the thermodynamically disfavored tautomer was attempted with acids and bases but could not be effected, indicating kinetic inhibition of proton transfer.

  4. Multidimensional Perovskites: A Mixed Cation Approach Towards Ambient Stable and Tunable Perovskite Photovoltaics. (United States)

    Koh, Teck Ming; Thirumal, Krishnamoorthy; Soo, Han Sen; Mathews, Nripan


    Although halide perovskites are able to deliver high power conversion efficiencies, their ambient stability still remains an obstacle for commercialization. Thus, promoting the ambient stability of perovskites has become a key research focus. In this review, we highlight the sources of instability in conventional 3 D perovskites, including water intercalation, ion migration, and thermal decomposition. Recently, the multidimensional perovskites approach has become one of the most promising strategies to enhance the stability of perovskites. As compared to pure 2 D perovskites, multidimensional perovskites typically possess more ideal band gaps, better charge transport, and lower exciton binding energy, which are essential for photovoltaic applications. The larger organic cations in multidimensional perovskites could also be more chemically stable at higher temperatures than the commonly used methylammonium cation. By combining 3 D and 2 D perovskites to form multidimensional perovskites, halide perovskite photovoltaics can attain both high efficiency and increased stability.

  5. Localization versus delocalization in diamine radical cations

    DEFF Research Database (Denmark)

    Brouwer, A.M.; Wiering, P.G.; Zwier, J.M.;


    The optical absorption spectrum of the radical cation of 1,4-diphenylpiperazine 2a shows a strong transition in the near-IR, and only a weak band at 445 nm, in the region where aniline radical cations normally absorb strongly. This indicates that the charge and spin are delocalized over the two...

  6. Nuclear reactions at intermediate energies

    Directory of Open Access Journals (Sweden)

    Shyam Radhey


    Full Text Available In the domain of Nuclear reactions at intermediate energies, the QCD coupling constant αs is large enough (~ 0.3 - 0.5 to render the perturbative calculational techniques inapplicable. In this regime the quarks are confined into colorless hadrons and it is expected that effective field theories of hadron interactions via exchange of hadrons, provide useful tools to describe such reactions. In this contribution we discuss the application of one such theory, the effective Lagrangian model, in describing the hadronic reactions at intermediate energies whose measurements are the focus of a vast international experimental program.

  7. Cation diffusion in the natural zeolite clinoptilolite

    Energy Technology Data Exchange (ETDEWEB)

    Dyer, A.; White, K.J. [Science Research Institute, Chemistry Division, Cockcroft Building, University of Salford, Salford (United Kingdom)


    The natural zeolite clinoptilolite is mined commercially in many parts of the world. It is a selective exchanger for the ammonium cation and this has prompted its use in waste water treatment, swimming pools and in fish farming. It is also used to scavenge radioisotopes in nuclear waste clean-up. Further potential uses for clinoptilolite are in soil amendment and remediation. The work described herein provides thermodynamic data on cation exchange processes in clinoptilolite involving the NH{sub 4}, Na, K, Ca, and Mg cations. The data includes estimates of interdiffusion coefficients together with free energies, entropies and energies of activation for the cation exchanges studied. Suggestions are made as to the mechanisms of cation-exchanges involved.

  8. 棘突间动态稳定装置Wallis治疗腰椎退行性疾病中长期随访效果分析%Intermediate and long-term follow-up evaluation of posterior dynamic lumbar stabilization in lumbar degenerative disease

    Institute of Scientific and Technical Information of China (English)

    徐林; 俞兴; 毕连涌; 柳根哲; 李鹏洋; 曲弋; 焦勇


    目的 探讨棘突间动态稳定装置Wallis治疗腰椎退行性疾病的中长期效果.方法 回顾性分析2007年8月至2010年1月采用Wallis或结合固定融合方法治疗腰椎退行性疾病并有2年以上随访的96例患者资料,其中男性51例,女性45例;年龄21 ~ 68岁,平均41.5岁.采用疼痛视觉模拟量表(VAS)1 00分法和中华医学会骨科分会脊柱外科学组腰椎手术疗效标准评估手术短期和中长期疗效,测量分析术前、术后3个月和末次随访时Wallis植入节段椎间盘终板高度,随访有无Wallis相关并发症及患者对手术的满意度,部分患者MRI检查分析Wallis植入节段术后椎间盘影像学变化.结果 术前、术后3个月及末次随访疼痛VAS评分分别为78 ±24、28±16和14±12,采用配对t检验,术后3个月及末次随访疼痛VAS评分较术前明显下降(t=2.634和2.653,P<0.01);末次随访疼痛VAS评分较术后3个月也有下降(t=2.147,P<0.05).术后末次随访功能恢复优良率为91.7%,患者手术整体满意率为95.8%,术前、术后3个月和末次随访时Wallis植入节段椎间盘终板高度分别为(8.2±3.7)、(10.4±2.6)和(10.1±1.9) mm,MRI检查未发现植入节段间盘退变加速、部分患者可见椎间盘水化.结论 棘突间动态稳定装置Wallis或结合固定融合方法治疗腰椎退行性疾病简便安全,2年以上中长期随访疗效良好,为腰椎退行性疾病的手术治疗增加了一种新的选择.%Objective To evaluate the intermediate and long-term follow-up effect of posterior dynamic lumbar stabilization in lumbar degenerative disease.Methods The clinical outcomes of 96 patients (male 51,female 45,age from 21 to 68 years,mean 41.5 years) whose follow-up time were more than 2 years with lumbar degenerative disease treated by posterior decompression with Wallis posterior dynamic lumbar stabilization implant or combined with posterior lumbar fusion from August 2007 to January 2010 were

  9. Natural zeolite reactivity towards ozone: The role of compensating cations

    Energy Technology Data Exchange (ETDEWEB)

    Valdes, Hector, E-mail: [Laboratorio de Tecnologias Limpias (F. Ingenieria), Universidad Catolica de la Santisima Concepcion, Alonso de Ribera 2850, Concepcion (Chile); Alejandro, Serguei; Zaror, Claudio A. [Departamento de Ingenieria Quimica (F. Ingenieria), Universidad de Concepcion, Concepcion (Chile)


    Highlights: Black-Right-Pointing-Pointer Chemical and thermal treatment enhances catalytic activity of natural zeolite. Black-Right-Pointing-Pointer Modified natural zeolite exhibits high stability after thermal treatment. Black-Right-Pointing-Pointer Reducing the compensating cation content leads to an increase on ozone abatement. Black-Right-Pointing-Pointer Surface active atomic oxygen was detected using the DRIFT technique. Black-Right-Pointing-Pointer The highest reactivity toward ozone was performed by NH4Z3 zeolite sample. - Abstract: Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L{sup -1}). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77 K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH{sub 3}-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal.

  10. Molecular Dynamics Study of a Dual-Cation Ionomer Electrolyte. (United States)

    Chen, Xingyu; Chen, Fangfang; Jónsson, Erlendur; Forsyth, Maria


    The poly(N1222 )x Li1-x [AMPS] ionomer system (AMPS=2-acrylamido-2-methylpropane sulfonic acid) with dual cations has previously shown decoupled Li ion dynamics from polymer segmental motions, characterized by the glass-transition temperature, which can result in a conductive electrolyte material whilst retaining an appropriate modulus (i.e. stiffness) so that it can suppress dendrite formation, thereby improving safety when used in lithium-metal batteries. To understand this ion dynamics behavior, molecular dynamics techniques have been used in this work to simulate structure and dynamics in these materials. These simulations confirm that the Li ion transport is decoupled from the polymer particularly at intermediate N1222(+) concentrations. At 50 mol % N1222(+) concentration, the polymer backbone is more rigid than for higher N1222(+) concentrations, but with increasing temperature Li ion dynamics are more significant than polymer or quaternary ammonium cation motions. Herein we suggest an ion-hopping mechanism for Li(+) , arising from structural rearrangement of ionic clusters that could explain its decoupled behavior. Higher temperatures favor an aggregated ionic structure as well as enhancing these hopping motions. The simulations discussed here provide an atomic-level understanding of ion dynamics that could contribute to designing an improved ionomer with fast ion transport and mechanical robustness.

  11. The lightest organic radical cation for charge storage in redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jinhua; Pan, Baofei; Duan, Wentao; Wei, Xiaoliang; Assary, Rajeev S.; Su, Liang; Brushett, Fikile; Cheng, Lei; Liao, Chen; Ferrandon, Magali S.; Wang, Wei; Zhang, Zhengcheng; Burrell, Anthony K.; Curtiss, Larry A.; Shkrob, Ilya A.; Moore, Jeffrey S.; Zhang, Lu


    Electrochemically reversible fluids of high energy density are promising materials for capturing the electrical energy generated from intermittent sources like solar and wind. To meet this technological challenge there is a need to understand the fundamental limits and interplay of electrochemical potential, stability and solubility in “lean” derivatives of redox-active molecules. Here we describe the process of molecular pruning, illustrated for 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene, a molecule known to produce a persistently stable, high-potential radical cation. By systematically shedding molecular fragments considered important for radical cation steric stabilization, we discovered a minimalistic structure that retains long-term stability in its oxidized form. Interestingly, we find the tert-butyl groups are unnecessary; high stability of the radical cation and high solubility are both realized in derivatives having appropriately positioned arene methyl groups. These stability trends are rationalized by mechanistic considerations of the postulated decomposition pathways. We suggest that the molecular pruning approach will uncover lean redox active derivatives for electrochemical energy storage leading to materials with long-term stability and high intrinsic capacity.

  12. Material Voices: Intermediality and Autism (United States)

    Trimingham, Melissa; Shaughnessy, Nicola


    Autism continues to be regarded enigmatically; a community that is difficult to access due to perceived disruptions of interpersonal connectedness. Through detailed observations of two children participating in the Arts and Humanities Research Council funded project "Imagining Autism: Drama, Performance and Intermediality as Interventions for…

  13. Association Mechanisms of Unsaturated C2 Hydrocarbons with Their Cations: Acetylene and Ethylene (United States)

    Bera, Partha P.; Head-Gordon, Martin; Lee, Timothy J.


    The ion-molecule association mechanism of acetylene and ethylene with their cations is investigated by ab initio quantum chemical methods to understand the structures, association energies, and the vibrational and electronic spectra of the products. Stable puckered cyclic isomers are found as the result of first forming less stable linear and bridge isomers. The puckered cyclic complexes are calculated to be strongly bound, by 87, 35 and 56 kcal/mol for acetylene-acetylene cation, ethylene-ethylene cation and acetylene-ethylene cation, respectively. These stable complexes may be intermediates that participate in further association reactions. There are no association barriers, and no significant inter-conversion barriers, so the initial linear and bridge encounter complexes are unlikely to be observable. However, the energy gap between the bridged and cyclic puckered isomers greatly differs from complex to complex: it is 44 kcal/mol in C4H4 +, but only 6 kcal/mol in C4H8 +. The accurate CCSD(T) calculations summarized above are also compared against less computationally expensive MP2 and density functional theory (DFT) calculations for structures, relative energies, and vibrational spectra. Calculated vibrational spectra are compared against available experiments for cyclobutadiene cation. Electronic spectra are also calculated using time-dependent DFT.

  14. Effect of alkali-treated lipopolysaccharide on the intracellular cations of human erythrocytes. (United States)

    Warren, J R; Kowalski, M M; Wallas, C H


    The adsorption to human erythrocytes of Escherichia coli lipopolysaccharide treated by mild alkaline hydrolysis (h-LPS) stimulated an increase in the intracellular Na+ concentration and a decrease in the intracellular K+ concentration of the erythrocytes. Erythrocytes treated by h-LPS remained responsive to the membrane adenosine triphosphatase inhibitors ouabain and ethacrynic acid, indicating that hLPS did not alter erythrocyte cations be depleting energy intermediates or uncoupling energy metabolism from active cation transport. The h-LPS-treated erythrocytes became non-agglutinable by the lectin concanavalin A prior to the development of changes in intracellular cations. In addition, h-LPS-treated erythrocytes demonstrated a three-fold greater cation response to ethacrynic acid than the untreated erythrocytes; this greater response was probably due to local membrane effects by h-LPS on the ethacrynic acid-sensitive adenosine triphosphatase. It is suggested that the h-LPS-induced alteration of erythrocyte cation content was secondary to an increase in ion permeability localized to the concanavalin A receptor regions of the erythrocyte membrane, possibly combined with indirect effects of membrane-bound h-LPS on ethacrynic acid-sensitive adenosine triphosphatase.

  15. Cationic Bolaamphiphiles for Gene Delivery (United States)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad


    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  16. Formation of cationic [RP5Cl](+)-cages via insertion of [RPCl](+)-cations into a P-P bond of the P4 tetrahedron. (United States)

    Holthausen, Michael H; Feldmann, Kai-Oliver; Schulz, Stephen; Hepp, Alexander; Weigand, Jan J


    Fluorobenzene solutions of RPCl(2) and a Lewis acid such as ECl(3) (E = Al, Ga) in a 1:1 ratio are used as reactive sources of chlorophosphenium cations [RPCl](+), which insert into P-P bonds of dissolved P(4). This general protocol represents a powerful strategy for the synthesis of new cationic chloro-substituted organophosphorus [RP(5)Cl](+)-cages as illustrated by the isolation of several monocations (21a-g(+)) in good to excellent yields. For singular reaction two possible reaction mechanisms are proposed on the basis of quantum chemical calculations. The intriguing NMR spectra and structures of the obtained cationic [RP(5)Cl](+)-cages are discussed. Furthermore, the reactions of dichlorophosphanes and the Lewis acid GaCl(3) in various stoichiometries are investigated to obtain a deeper understanding of the species involved in these reactions. The formation of intermediates such as RPCl(2)·GaCl(3) (14) adducts, dichlorophosphanylchlorophosphonium cations [RPCl(2)-RPCl](+) (16(+)) and [RPCl(2)-RPCl-GaCl(3)](+) (17(+)) in reaction mixtures of RPCl(2) and GaCl(3) in fluorobenzene strongly depends on the basicity of the dichlorophosphane RPCl(2) (R = tBu, Cy, iPr, Et, Me, Ph, C(6)F(5)) and the reaction stoichiometry.

  17. Ion-radical intermediates of the radiation-chemical transformations of organic carbonates (United States)

    Shiryaeva, Ekaterina S.; Sosulin, Ilya S.; Saenko, Elizaveta V.; Feldman, Vladimir I.


    The spectral features and reactions of ion-radical intermediates produced from organic carbonates in low-temperature matrices were investigated by EPR spectroscopy and quantum-chemical calculations. It was shown that radical cations of diethyl carbonate and dimethyl carbonate underwent intramolecular hydrogen transfer to yield alkyl-type species, as was suggested previously. Meanwhile, radical cation of EC demonstrates a ring cleavage even at 77 K, while radical cation of PC is probably intrinsically stable and undergo an ion-molecule reaction with a neighboring neutral molecule in dimers or associates. Radical anions were obtained in glassy matrices of diethyl ether or perdeuteroethanol. The radical anions of linear carbonates show photoinduced fragmentation to yield the corresponding alkyl radicals; such process may also occur directly under radiolysis. Radical anions of cyclic carbonates are relatively stable and yield only trace amounts of fragmentation products under similar conditions.

  18. Cation distributions on rapidly solidified cobalt ferrite (United States)

    De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.


    The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

  19. Quantum mechanical investigations on the role of neutral and negatively charged enamine intermediates in organocatalyzed reactions

    Energy Technology Data Exchange (ETDEWEB)

    Hubin, Pierre O., E-mail: [Laboratoire de Physico-Chimie Informatique (PCI), Unité de Chimie Physique Théorique et Structurale, University of Namur, 61 rue de Bruxelles, 5000 Namur (Belgium); Jacquemin, Denis [Laboratoire CEISAM – UMR CNRS 6230, Université de Nantes, 2 rue de la Houssinière, BP92208, 44322 Nantes Cedex 3 (France); Institut Universitaire de France 103, Boulevard St Michel, 75005 Paris Cedex 5 (France); Leherte, Laurence; Vercauteren, Daniel P. [Laboratoire de Physico-Chimie Informatique (PCI), Unité de Chimie Physique Théorique et Structurale, University of Namur, 61 rue de Bruxelles, 5000 Namur (Belgium)


    Highlights: • M06-2X functional is suitable to model key steps of proline-catalyzed reactions. • Investigation of the proline-catalyzed aldol reaction mechanism. • Influence of water molecules on the C–C bond formation step. • Mechanism for the reaction of proline-derived enamines with benzhydrylium cations. - Abstract: The proline-catalyzed aldol reaction is the seminal example of asymmetric organocatalysis. Previous theoretical and experimental studies aimed at identifying its mechanism in order to rationalize the outcome of this reaction. Here, we focus on key steps with modern first principle methods, i.e. the M06-2X hybrid exchange–correlation functional combined to the solvation density model to account for environmental effects. In particular, different pathways leading to the formation of neutral and negatively charged enamine intermediates are investigated, and their reactivity towards two electrophiles, i.e. an aldehyde and a benzhydrylium cation, are compared. Regarding the self-aldol reaction, our calculations confirm that the neutral enamine intermediate is more reactive than the negatively charged one. For the reaction with benzhydrylium cations however, the negatively charged enamine intermediate is more reactive.

  20. Larval helminths in intermediate hosts

    DEFF Research Database (Denmark)

    Fredensborg, Brian Lund; Poulin, R


    Density-dependent effects on parasite fitness have been documented from adult helminths in their definitive hosts. There have, however, been no studies on the cost of sharing an intermediate host with other parasites in terms of reduced adult parasite fecundity. Even if larval parasites suffer...... a reduction in size, caused by crowding, virtually nothing is known about longer-lasting effects after transmission to the definitive host. This study is the first to use in vitro cultivation with feeding of adult trematodes to investigate how numbers of parasites in the intermediate host affect the size...... and fecundity of adult parasites. For this purpose, we examined two different infracommunities of parasites in crustacean hosts. Firstly, we used experimental infections of Maritrema novaezealandensis in the amphipod, Paracalliope novizealandiae, to investigate potential density-dependent effects in single...

  1. Cationic ruthenium alkylidene catalysts bearing phosphine ligands. (United States)

    Endo, Koji; Grubbs, Robert H


    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

  2. Cation locations and dislocations in zeolites (United States)

    Smith, Luis James

    The focus of this dissertation is the extra-framework cation sites in a particular structural family of zeolites, chabazite. Cation sites play a particularly important role in the application of these sieves for ion exchange, gas separation, catalysis, and, when the cation is a proton, acid catalysis. Structural characterization is commonly performed through the use of powder diffraction and Rietveld analysis of powder diffraction data. Use of high-resolution nuclear magnetic resonance, in the study of the local order of the various constituent nuclei of zeolites, complements well the long-range order information produced by diffraction. Recent developments in solid state NMR techniques allow for increased study of disorder in zeolites particularly when such phenomena test the detection limits of diffraction. These two powerful characterization techniques, powder diffraction and NMR, offer many insights into the complex interaction of cations with the zeolite framework. The acids site locations in SSZ-13, a high silica chabazite, and SAPO-34, a silicoaluminophosphate with the chabazite structure, were determined. The structure of SAPO-34 upon selective hydration was also determined. The insensitivity of X-rays to hydrogen was avoided through deuteration of the acid zeolites and neutron powder diffraction methods. Protons at inequivalent positions were found to have different acid strengths in both SSZ-13 and SAPO-34. Other light elements are incorporated into zeolites in the form of extra-framework cations, among these are lithium, sodium, and calcium. Not amenable by X-ray powder diffraction methods, the positions of such light cations in fully ion-exchanged versions of synthetic chabazite were determined through neutron powder diffraction methods. The study of more complex binary cation systems were conducted. Powder diffraction and solid state NMR methods (MAS, MQMAS) were used to examine cation site preferences and dislocations in these mixed-akali chabazites

  3. Cationized Carbohydrate Gas-Phase Fragmentation Chemistry (United States)

    Bythell, Benjamin J.; Abutokaikah, Maha T.; Wagoner, Ashley R.; Guan, Shanshan; Rabus, Jordan M.


    We investigate the fragmentation chemistry of cationized carbohydrates using a combination of tandem mass spectrometry, regioselective labeling, and computational methods. Our model system is D-lactose. Barriers to the fundamental glyosidic bond cleavage reactions, neutral loss pathways, and structurally informative cross-ring cleavages are investigated. The most energetically favorable conformations of cationized D-lactose were found to be similar. In agreement with the literature, larger group I cations result in structures with increased cation coordination number which require greater collision energy to dissociate. In contrast with earlier proposals, the B n -Y m fragmentation pathways of both protonated and sodium-cationized analytes proceed via protonation of the glycosidic oxygen with concerted glycosidic bond cleavage. Additionally, for the sodiated congeners our calculations support sodiated 1,6-anhydrogalactose B n ion structures, unlike the preceding literature. This affects the subsequent propensity of formation and prediction of B n /Y m branching ratio. The nature of the anomeric center (α/β) affects the relative energies of these processes, but not the overall ranking. Low-energy cross-ring cleavages are observed for the metal-cationized analytes with a retro-aldol mechanism producing the 0,2 A 2 ion from the sodiated forms. Theory and experiment support the importance of consecutive fragmentation processes, particularly for the protonated congeners at higher collision energies.

  4. Covalent functionalization of graphene with reactive intermediates. (United States)

    Park, Jaehyeung; Yan, Mingdi


    Graphene, a material made exclusively of sp(2) carbon atoms with its π electrons delocalized over the entire 2D network, is somewhat chemically inert. Covalent functionalization can enhance graphene's properties including opening its band gap, tuning conductivity, and improving solubility and stability. Covalent functionalization of pristine graphene typically requires reactive species that can form covalent adducts with the sp(2) carbon structures in graphene. In this Account, we describe graphene functionalization reactions using reactive intermediates of radicals, nitrenes, carbenes, and arynes. These reactive species covalently modify graphene through free radical addition, CH insertion, or cycloaddition reactions. Free radical additions are among the most common reaction, and these radicals can be generated from diazonium salts and benzoyl peroxide. Electron transfer from graphene to aryl diazonium ion or photoactivation of benzoyl peroxide yields aryl radicals that subsequently add to graphene to form covalent adducts. Nitrenes, electron-deficient species generated by thermal or photochemical activation of organic azides, can functionalize graphene very efficiently. Because perfluorophenyl nitrenes show enhanced bimolecular reactions compared with alkyl or phenyl nitrenes, perfluorophenyl azides are especially effective. Carbenes are used less frequently than nitrenes, but they undergo CH insertion and C═C cycloaddition reactions with graphene. In addition, arynes can serve as a dienophile in a Diels-Alder type reaction with graphene. Further study is needed to understand and exploit the chemistry of graphene. The generation of highly reactive intermediates in these reactions leads to side products that complicate the product composition and analysis. Fundamental questions remain about the reactivity and regioselectivity of graphene. The differences in the basal plane and the undercoordinated edges of graphene and the zigzag versus arm-chair configurations

  5. An overview of quantification methods in energy-dispersive X-ray fluorescence analysis

    Indian Academy of Sciences (India)

    A Markowicz


    This paper reviews the major factors influencing the accuracy of the energy-dispersive X-ray fluorescence (EDXRF) analysis including physical and chemical matrix effects (resulting from particle size, surface irregularity, mineralogy, moisture, absorption and enhancement) as well as the correction procedures with emphasis on the analysis of unprepared samples. Quantification methods for thin samples, samples with intermediate thickness and thick samples are presented including fundamental parameter methods, influence coefficient algorithms, empirical coefficient algorithms and quantification methods based on scattered primary radiation. Quality control procedures are also reviewed.

  6. Cationic bis-N-heterocyclic carbene (NHC) ruthenium complex: structure and application as latent catalyst in olefin metathesis. (United States)

    Rouen, Mathieu; Queval, Pierre; Falivene, Laura; Allard, Jessica; Toupet, Loïc; Crévisy, Christophe; Caijo, Frédéric; Baslé, Olivier; Cavallo, Luigi; Mauduit, Marc


    An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2 -NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions.

  7. Cationic bis-N-heterocyclic carbene (NHC) ruthenium complex: Structure and application as latent catalyst in olefin metathesis

    KAUST Repository

    Rouen, Mathieu


    An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions.

  8. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation (United States)

    Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi


    Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

  9. Role of Intermediate Filaments in Vesicular Traffic

    Directory of Open Access Journals (Sweden)

    Azzurra Margiotta


    Full Text Available Intermediate filaments are an important component of the cellular cytoskeleton. The first established role attributed to intermediate filaments was the mechanical support to cells. However, it is now clear that intermediate filaments have many different roles affecting a variety of other biological functions, such as the organization of microtubules and microfilaments, the regulation of nuclear structure and activity, the control of cell cycle and the regulation of signal transduction pathways. Furthermore, a number of intermediate filament proteins have been involved in the acquisition of tumorigenic properties. Over the last years, a strong involvement of intermediate filament proteins in the regulation of several aspects of intracellular trafficking has strongly emerged. Here, we review the functions of intermediate filaments proteins focusing mainly on the recent knowledge gained from the discovery that intermediate filaments associate with key proteins of the vesicular membrane transport machinery. In particular, we analyze the current understanding of the contribution of intermediate filaments to the endocytic pathway.

  10. Intermedial Strategies of Memory in Contemporary Novels

    DEFF Research Database (Denmark)

    Tanderup, Sara


    In her article "Intermedial Strategies and Memory in Contemporary Novels" Sara Tanderup discusses a tendency in contemporary literature towards combining intermedial experiments with a thematic preoccupation with memory and trauma. Analyzing selected works by Steven Hall, Jonathan Safran Foer...

  11. Intermediate Filaments in Caenorhabditis elegans. (United States)

    Zuela, Noam; Gruenbaum, Yosef


    More than 70 different genes in humans and 12 different genes in Caenorhabditis elegans encode the superfamily of intermediate filament (IF) proteins. In C. elegans, similar to humans, these proteins are expressed in a cell- and tissue-specific manner, can assemble into heteropolymers and into 5-10nm wide filaments that account for the principal structural elements at the nuclear periphery, nucleoplasm, and cytoplasm. At least 5 of the 11 cytoplasmic IFs, as well as the nuclear IF, lamin, are essential. In this chapter, we will include a short review of our current knowledge of both cytoplasmic and nuclear IFs in C. elegans and will describe techniques used for their analyses.

  12. ESL intermediate/advanced writing

    CERN Document Server

    Munoz Page, Mary Ellen; Jaskiewicz, Mary


    Master ESL (English as a Second Language) Writing with the study guide designed for non-native speakers of English. Skill-building lessons relevant to today's topics help ESL students write complete sentences, paragraphs, and even multi-paragraph essays. It's perfect for classroom use or self-guided writing preparation.DETAILS- Intermediate drills for improving skills with parallel structure, mood, correct shifting errors & dangling participles- Advanced essay drills focusing on narrative, descriptive, process, reaction, comparison and contrast- Superb preparation for students taking the TOEFL

  13. The sequence to hydrogenate coronene cations: A journey guided by magic numbers

    CERN Document Server

    Cazaux, Stéphanie; Rougeau, Nathalie; Reitsma, Geert; Hoekstra, Ronnie; Teillet-Billy, Dominique; Morisset, Sabine; Spaans, Marco; Schlathölter, Thomas


    The understanding of hydrogen attachment to carbonaceous surfaces is essential to a wide variety of research fields and technologies such as hydrogen storage for transportation, precise localization of hydrogen in electronic devices and the formation of cosmic H2. For coronene cations as prototypical Polycyclic Aromatic Hydrocarbon (PAH) molecules, the existence of magic numbers upon hydrogenation was uncovered experimentally. Quantum chemistry calculations show that hydrogenation follows a site-specific sequence leading to the appearance of cations having 5, 11, or 17 hydrogen atoms attached, exactly the magic numbers found in the experiments. For these closed-shell cations, further hydrogenation requires appreciable structural changes associated with a high transition barrier. Controlling specific hydrogenation pathways would provide the possibility to tune the location of hydrogen attachment and the stability of the system. The sequence to hydrogenate PAHs, leading to PAHs with magic numbers of H atoms att...

  14. Synthesis and Characterization of Zirconia Nanocrystallites by Cationic Surfactant and Anionic Surfactant

    Institute of Scientific and Technical Information of China (English)


    Study on nanomaterials has attracted great interests in recent years. In this article,zirconia nanocrystallites of different structures have been successfully synthesized via hydrothermal methods with cationic surfactant (CTAB) and anionic surfactant (SDS), respectively. Differential Scanning Calorimeter (DSC-TG), X-ray Diffractometer (XRD), Transmission Electron Microscope (TEM), Ultraviolet-Visible (UV-vis) and N2 adsorption-desorption analyses are used for their structure characteristics. The results show that the cationic surfactant has a distinctive direction effect on the formation of zirconia nanocrystallites, while the anionic surfactant has a self-assembly synergistic effect on them. The sample synthesized with the cationic surfactant presents good dispersion with the main phase of tetragonal zirconia, and the average nanocryst al size is around 15nm after calcination at 500 ℃. While the sample synthesized with the anionic surfactant exhibits a worm-like mesoporous structure with pure tetragonal phase after calcination at 500 ℃ and with good thermal stability.

  15. Cationic Pd(II-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

    Directory of Open Access Journals (Sweden)

    Takashi Nishikata


    Full Text Available Cationic palladium(II complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN4](BF42 or a nitrile-free cationic palladium(II complex generated in situ from the reaction of Pd(OAc2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1 C–H activation to generate a cationic palladacycle; (2 reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3 regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied.

  16. Cationic Pd(II)-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies (United States)

    Nishikata, Takashi; Abela, Alexander R; Huang, Shenlin


    Summary Cationic palladium(II) complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN)4](BF4)2 or a nitrile-free cationic palladium(II) complex generated in situ from the reaction of Pd(OAc)2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1) C–H activation to generate a cationic palladacycle; (2) reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3) regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II) complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied. PMID:27340491

  17. 34 CFR 200.17 - Intermediate goals. (United States)


    ... 34 Education 1 2010-07-01 2010-07-01 false Intermediate goals. 200.17 Section 200.17 Education... Programs Operated by Local Educational Agencies Adequate Yearly Progress (ayp) § 200.17 Intermediate goals. Each State must establish intermediate goals that increase in equal increments over the period...

  18. Intermediate-Mass Black Holes

    CERN Document Server

    Miller, M C


    The mathematical simplicity of black holes, combined with their links to some of the most energetic events in the universe, means that black holes are key objects for fundamental physics and astrophysics. Until recently, it was generally believed that black holes in nature appear in two broad mass ranges: stellar-mass (roughly 3-20 solar masses), which are produced by the core collapse of massive stars, and supermassive (millions to billions of solar masses), which are found in the centers of galaxies and are produced by a still uncertain combination of processes. In the last few years, however, evidence has accumulated for an intermediate-mass class of black holes, with hundreds to thousands of solar masses. If such objects exist they have important implications for the dynamics of stellar clusters, the formation of supermassive black holes, and the production and detection of gravitational waves. We review the evidence for intermediate-mass black holes and discuss future observational and theoretical work t...

  19. Influence of the Ion Coordination Number on Cation Exchange Reactions with Copper Telluride Nanocrystals

    CERN Document Server

    Tu, Renyong; Bertoni, Giovanni; Lak, Aidin; Gaspari, Roberto; Rapallo, Arnaldo; Cavalli, Andrea; De Trizio, Luca; Manna, Liberato


    Cu2-xTe nanocubes were used as starting seeds to access metal telluride nanocrystals by cation exchanges at room temperature. The coordination number of the entering cations was found to play an important role in dictating the reaction pathways. The exchanges with tetrahedrally coordinated cations (i.e. with coordination number 4), such as Cd2+ or Hg2+, yielded monocrystalline CdTe or HgTe nanocrystals with Cu2-xTe/CdTe or Cu2-xTe/HgTe Janus-like heterostructures as intermediates. The formation of Janus-like architectures was attributed to the high diffusion rate of the relatively small tetrahedrally coordinated cations, which could rapidly diffuse in the Cu2-xTe NCs and nucleate the CdTe (or HgTe) phase in a preferred region of the host structure. Also, with both Cd2+ and Hg2+ ions the exchange led to wurtzite CdTe and HgTe phases rather than the more stable zinc-blende ones, indicating that the anion framework of the starting Cu2- xTe particles could be more easily deformed to match the anion framework of t...

  20. H2O Nucleation Around Noble Metal Cations (United States)

    Calaminici, Patrizia; Oropeza Alfaro, Pavel; Juarez Flores, Martin; Köster, Andreas; Beltran, Marcela; Ulises Reveles, J.; Khanna, Shiv N.


    First principle electronic structure calculations have been carried out to investigate the ground state geometry, electronic structure and binding energy of noble metal cations (H2O)n^+ clusters containing up to 10 H2O molecules. The calculations are performed with the density functional theory code deMon2k [1]. Due to the very flat potential energy surface of these systems special care to the numerical stability of energy and gradient calculation must be taken.Comparison of the results obtained with Cu^+, Ag^+ and Au^+ will be shown. This investigation provides insight into the structural arrangement of the water molecules around these metals and a microscopic understanding of the observed incremental binding energy in the case of the gold cation based on collision induced dissociation experiments. [1] A.M. Köster, P. Calaminici, M.E. Casida, R. Flores-Moreno, G. Geudtner, A. Goursot, T. Heine, A. Ipatov, F. Janetzko, J. Martin del Campo, S. Patchkovski, J.U. Reveles, A. Vela and D.R. Salahub, deMon2k, The deMon Developers, Cinvestav, 2006

  1. Intermediate view synthesis from stereoscopic images

    Institute of Scientific and Technical Information of China (English)

    Lü Chaohui; An Ping; Zhang Zhaoyang


    A new method is proposed for synthesizing intermediate views from a pair of stereoscopic images. In order to synthesize high-quality intermediate views, the block matching method together with a simplified multi-window technique and dynamic programming is used in the process of disparity estimation. Then occlusion detection is performed to locate occluded regions and their disparities are compensated. After the projecton of the left-to-right and right-to-left disparities onto the intermediate image, intermediate view is synthesized considering occluded regions. Experimental results show that our synthesis method can obtain intermediate views with higher quality.

  2. Corrosion inhibitors for intermediate cooling systems

    Energy Technology Data Exchange (ETDEWEB)

    Falk, I.; Suhr, L.


    The selected inhibitors were tested for heat and radiation stability and corrosion protection on the bench scale. Based on the results from these tests two of the products were selected, Bycoguard 81 and Bycoguard MP4S for continuing corrosion tests in an autoclave loop at 90 degrees C and 120 degrees C. Oxygen saturated deionized water with an addition of 1 ppm chloride was recirculated in the loop. Samples of copper and carbon steel were exposed to the water in the autoclave for periods up to 10 weeks. The purpose of this project was to find a substitute for hydrazine and chromates. Besides good corrosion protection qualities the toxic and environmental effect of the inhibitors should be minimal. The investigation has shown that the copper inhibitor BTA (benzotriazole) loses its corrosion protection qualities at a water temperature of 120 degrees C. The protection effects at 90 degrees C were satisfactory for both of the materials. The corrosion rates measured were 0.01 mm/y or less for the copper and carbon steel samples. The environment in the autoclave during the testing was more corrosive than is to be found in intermediate cooling systems. Due to the low corrosion rates measured the two inhibitors are to be recommended as alternatives to hydrazine and chromates.

  3. Hemin/G-quadruplex structure and activity alteration induced by magnesium cations. (United States)

    Kosman, J; Juskowiak, B


    The influence of metal cations on G-quadruplex structure and peroxidase-mimicking DNAzyme activity was investigated. Experiments revealed a significant role of magnesium ion, which in the presence of potassium cation influenced DNAzyme activity. This ability has been associated with alteration of G-quadruplex topology and consequently affinity to bind hemin molecule. It has been demonstrated that G-quadruplex based on PS2.M sequence under these conditions formed parallel topology, which exhibited lower activity than that observed in standard potassium-containing solution. On the other hand DNAzyme/magnesium ion system based on telomeric sequence, which did not undergo significant structural changes, exhibited higher peroxidase activity upon magnesium ion addition. In both cases, the stabilization effect of magnesium cations on G-quadruplex structure was observed. The mechanism of DNAzyme activity alteration by magnesium ion can be explained by its influence on the pKa value of DNAzyme. Magnesium ion decreased pKa for PS2.M based system but increased it for telomeric DNAzyme. Magnesium cation effect on G-quadruplex structure as well as DNAzyme activity is particularly important since this ion is one of the most common metal cations in biological samples.

  4. Hybrid Perovskite Light-Emitting Diodes Based on Perovskite Nanocrystals with Organic-Inorganic Mixed Cations. (United States)

    Zhang, Xiaoli; Liu, He; Wang, Weigao; Zhang, Jinbao; Xu, Bing; Karen, Ke Lin; Zheng, Yuanjin; Liu, Sheng; Chen, Shuming; Wang, Kai; Sun, Xiao Wei


    Organic-inorganic hybrid perovskite materials with mixed cations have demonstrated tremendous advances in photovoltaics recently, by showing a significant enhancement of power conversion efficiency and improved perovskite stability. Inspired by this development, this study presents the facile synthesis of mixed-cation perovskite nanocrystals based on FA(1-x) Csx PbBr3 (FA = CH(NH2 )2 ). By detailed characterization of their morphological, optical, and physicochemical properties, it is found that the emission property of the perovskite, FA(1-x) Csx PbBr3 , is significantly dependent on the substitution content of the Cs cations in the perovskite composition. These mixed-cation perovskites are employed as light emitters in light-emitting diodes (LEDs). With an optimized composition of FA0.8 Cs0.2 PbBr3 , the LEDs exhibit encouraging performance with a highest reported luminance of 55 005 cd m(-2) and a current efficiency of 10.09 cd A(-1) . This work provides important instructions on the future compositional optimization of mixed-cation perovskite for obtaining high-performance LEDs. The authors believe this work is a new milestone in the development of bright and efficient perovskite LEDs.

  5. Adsorption of mixed cationic-nonionic surfactant and its effect on bentonite structure

    Institute of Scientific and Technical Information of China (English)

    Yaxin Zhang; Yan Zhao; Yong Zhu; Huayong Wu; Hongtao Wang; Wenjing Lu


    The adsorption of cationic-nordonic mixed surfactant onto bentonite and its effect on bentonite structure were investigated.The objective was to improve the understanding of surfactant behavior on clay mineral for its possible use in remediation technologies of soil and groundwater contaminated by toxic organic compounds.The cationic surfactant used was hexadecylpyridinium bromide(HDPB),and the nonionic suffactant was Triton X-100(TX100).Adsorption of TX100 was enhanced significantly by the addition of HDPB,but this enhancement decreased with an increase in the fraction of the cationic surfactant.Part of HDPB was replaced by TX100 which decreased the adsorption of HDPB.However,the total adsorbed amount of the mixed surfactant was still increased substantially,indicating the synergistic effect between the cationic and nonionic surfactants.The surfactant-modified bentonite was characterized by Brunauer-Emmett-Teller specific surface area measurement,Fourier transform infrared spectroscopy,and thermogravimetric-derivative thermogravimetric/differential thermal analyses.Surfactant intercalation was found to decrease the bentonite specific surface area,pore volume,and surface roughness and irregularities,as calculated by nitrogen adsorption-desorption isotherms.The co-adsorption of the cationic and nonionic surfactants increased the ordering conformation of the adsorbed surfactants on bentonite,but decreased the thermal stability of the organobentonite system.

  6. Living cationic polymerization and polyhomologation: an ideal combination to synthesize functionalized polyethylene–polyisobutylene block copolymers

    KAUST Repository

    Zhang, Hefeng


    A series of hydroxyl-terminated polyisobutylene-b-polyethylene (PIB-b-PE-OH) copolymers were synthesized by combining living cationic polymerization and polyhomologation. Allyl-terminated PIBs, synthesized by living cationic polymerization, were hydroborated with BH3·THF to produce 3-arm boron-linked stars, PIB3B, which served as macroinitiators for the in situ polyhomologation of dimethylsulfoxonium methylide. The resulting 3-arm star block copolymers, (PIB-b-PE)3B, were oxidized/hydrolysed to afford PIB-b-PE-OH. Characterization of all intermediates and final products by high temperature gel permeation chromatography (HT-GPC) and proton nuclear magnetic resonance spectroscopy (1H NMR) revealed the well-defined character of the copolymers. The thermal properties of the copolymers were studied by differential scanning calorimetry (DSC).

  7. A spectroscopic study of interaction of cationic dyes with heparin

    Directory of Open Access Journals (Sweden)

    R. Nandini


    Full Text Available The interaction of two cationic dyes namely, acridine orange and pinacyanol chloride with an anionic polyelectrolyte, heparin, has been investigated by spectrophotometric method.The polymer induced metachromasy in the dyes resulting in the shift of the absorption maxima of the dyes towards shorter wavelengths. The stability of the complexes formed between acridine orange and heparin was found to be lesser than that formed between pinacyanol chloride and heparin. This fact was further confirmed by reversal studies using alcohols, urea and surfactants. The interaction of acridine orange with heparin has also been investigated fluorimetrically.The interaction parameters revealed that binding between acridine orange and heparin arises due to electrostatic interaction while that between pinacyanol chloride and heparin is found to involve both electrostatic and hydrophobic forces. The effect of the structure of the dye in inducing metachromasy has also been discussed.

  8. Cation Effect on Copper Chemical Mechanical Polishing

    Institute of Scientific and Technical Information of China (English)

    WANG Liang-Yong; LIU Bo; SONG Zhi-Tang; FENG Song-Lin


    We examine the effect of cations in solutions containing benzotriazole (BTA) and H2O2 on copper chemical mechanical polishing (CMP). On the base of atomic force microscopy (AFM) and material removal rate (MRR) results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demon-strates the worst performance. These results reveal a mechanism that sma//molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential (OCP).

  9. Cation Effect on Copper Chemical Mechanical Polishing (United States)

    Wang, Liang-Yong; Liu, Bo; Song, Zhi-Tang; Feng, Song-Lin


    We examine the effect of cations in solutions containing benzotriazole (BTA) and H2O2 on copper chemical mechanical polishing (CMP). On the base of atomic force microscopy (AFM) and material removal rate (MRR) results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demonstrates the worst performance. These results reveal a mechanism that small molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential (OCP).

  10. Cationically polymerizable monomers derived from renewable sources

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.


    The objectives of this project are to design and synthesize novel monomers which orginate from renewable biological sources and to carry out their rapid, efficient, pollution-free and energy efficient cationic polymerization to useful products under the influence of ultraviolet light or heat. A summary of the results of the past year's research on cationically polymerizable monomers derived from renewable sources is presented. Three major areas of investigation corresponding to the different classes of naturally occurring starting materials were investigated; epoxidized terpenes and natural rubber and vinyl ethers from alcohols and carbohydrates.

  11. Monomer and dimer radical cations of benzene, toluene, and naphthalene. (United States)

    Das, Tomi Nath


    Pulse radiolytic generation of monomeric and dimeric cations of benzene, toluene, and naphthalene in aqueous acid media at room temperature and their spectrophotometric characterization is discussed. Results presented include measurements of each aromatic's solubility in H(2)O-H(2)SO(4) and H(2)O-HClO(4) media over the acidity range pH 1 to H(0) -7.0, facile oxidative generation, and real-time identification of appropriate cationic transients with respective lambda(max) (nm) and epsilon (M(-1) cm(-1)) values measured as follows: C(6)H(6)(*+) (443, 1145 +/- 75), C(6)H(5)CH(3)(*+) (428, 1230 +/- 90), C(10)H(8)(*+) (381, 3650 +/- 225, and 687, 2210 +/- 160), (C(6)H(6))(2)(*+) (860, 2835 +/- 235), (C(6)H(5)CH(3))(2)(*+) (950, 1685 +/- 155), and (C(10)H(8))(2)(*+) (1040, 4170 +/- 320). Kinetic measurements reveal the respective formation rates of monomeric cations to be near-diffusion controlled, while the forward rate values for the dimeric species generation are marginally slower. The proton activity corrected pK(a) values are found to remain between -2.6 and -1.3 for the ArH(*+) species (C(6)H(6)(*+) most acidic, C(10)H(8)(*+) least acidic), while the pK(a) values of (ArH)(2)(*+) species vary from -5.0 to -3.0 ((C(6)H(6))(2)(*+) most acidic, (C(10)H(8))(2)(*+) least acidic). In H(0) -5 in aqueous H(2)SO(4), the respective stabilization energy of (C(6)H(6))(2)(*+), (C(6)H(5)CH(3))(2)(*+), and (C(10)H(8))(2)(*+) is estimated to be 16.6, 15.0, and 13.7 kcal mol(-1). Thus, the aqueous acid solution emerges as an alternative medium for typical radical-cationic studies, while offering compatibility for the deprotonated radical characterization near neutral pH.

  12. Intermediate inflation from rainbow gravity

    CERN Document Server

    Barrow, John D


    It is possible to dualize theories based on deformed dispersion relations and Einstein gravity so as to map them into theories with trivial dispersion relations and rainbow gravity. This often leads to "dual inflation" without the usual breaking of the strong energy condition. We identify the dispersion relations in the original frame which map into "intermediate" inflationary models. These turn out to be particularly simple: power-laws modulated by powers of a logarithm. The fluctuations predicted by these scenarios are near, but not exactly scale-invariant, with a red running spectral index. These dispersion relations deserve further study within the context of quantum gravity and the phenomenon of dimensional reduction in the ultraviolet.

  13. Displays for future intermediate UAV (United States)

    Desjardins, Daniel; Metzler, James; Blakesley, David; Rister, Courtney; Nuhu, Abdul-Razak


    The Dedicated Autonomous Extended Duration Airborne Long-range Utility System (DAEDALUS) is a prototype Unmanned Aerial Vehicle (UAV) that won the 2007 AFRL Commander's Challenge. The purpose of the Commander's Challenge was to find an innovative solution to urgent warfighter needs by designing a UAV with increased persistence for tactical employment of sensors and communication systems. DAEDALUS was chosen as a winning prototype by AFRL, AFMC and SECAF. Follow-on units are intended to fill an intermediate role between currently fielded Tier I and Tier II UAV's. The UAV design discussed in this paper, including sensors and displays, will enter Phase II for Rapid Prototype Development with the intent of developing the design for eventual production. This paper will discuss the DAEDALUS UAV prototype system, with particular focus on its communications, to include the infrared sensor and electro-optical camera, but also displays, specifically man-portable.

  14. Intermediate Jacobians of moduli spaces

    CERN Document Server

    Arapura, D; Arapura, Donu; Sastry, Pramathanath


    Let $SU_X(n,L)$ be the moduli space of rank n semistable vector bundles with fixed determinant L on a smooth projective genus g curve X. Let $SU_X^s(n,L)$ denote the open subset parametrizing stable bundles. We show that if g>3 and n > 1, then the mixed Hodge structure on $H^3(SU_X^s(n, L))$ is pure of type ${(1,2),(2,1)}$ and it carries a natural polarization such that the associated polarized intermediate Jacobian is isomorphic J(X). This is new when deg L and n are not coprime. As a corollary, we obtain a Torelli theorem that says roughly that $SU_X^s(n,L)$ (or $SU_X(n,L)$) determines X. This complements or refines earlier results of Balaji, Kouvidakis-Pantev, Mumford-Newstead, Narasimhan-Ramanan, and Tyurin.

  15. A kinetic study of ferrocenium cation decomposition utilizing an integrated electrochemical methodology composed of cyclic voltammetry and amperometry. (United States)

    Singh, Archana; Chowdhury, Debarati Roy; Paul, Amit


    A novel, easy, quick, and inexpensive integrated electrochemical methodology composed of cyclic voltammetry and amperometry has been developed for the determination of the kinetic stability of higher oxidation states for inorganic complexes. In this study, ferrocene and its derivatives have been used as model systems and the corresponding ferrocenium cations were generated in situ during the electrochemical experiments to determine their kinetic stabilities. The study found that the ferrocenium cations decompose following the first-order kinetics at 27 ± 3 °C in the presence of ambient oxygen and water. The half-lives of the ferrocenium, carboxylate ferrocenium, and decamethyl ferrocenium cations were found to be 1.27 × 10(3), 1.52 × 10(3), and ≫11.0 × 10(3) s, respectively, in acetonitrile solvent having a 0.5 M tetrabutylammonium hexafluorophosphate electrolyte. These results are in agreement with the previous reports, i.e. the ferrocenium cation is unstable whereas the decamethyl ferrocenium cation has superior stability. The new methodology has been established by performing various experiments using different concentrations of ferrocene, variable scan rates in cyclic voltammetry, different time periods for amperometry, and in situ spectroelectrochemical experiments.

  16. Advancements in the Synthesis and Applications of Cationic N-Heterocycles through Transition Metal-Catalyzed C-H Activation. (United States)

    Gandeepan, Parthasarathy; Cheng, Chien-Hong


    Cationic N-heterocycles are an important class of organic compounds largely present in natural and bioactive molecules. They are widely used as fluorescent dyes for biological studies, as well as in spectroscopic and microscopic methods. These compounds are key intermediates in many natural and pharmaceutical syntheses. They are also a potential candidate for organic light-emitting diodes (OLEDs). Because of these useful applications, the development of new methods for the synthesis of cationic N-heterocycles has received a lot of attention. In particular, many C-H activation methodologies that realize high step- and atom-economies toward these compounds have been developed. In this review, recent advancements in the synthesis and applications of cationic N-heterocycles through C-H activation reactions are summarized. The new C-H activation reactions described in this review are preferred over their classical analogs.

  17. Carbocations generated under stable conditions by ionization of matrix-Isolated radicals: the allyl and benzyl cations


    Mišić, Vladimir; Piech, Krzysztof; Bally, Thomas


    Carbocations are crucial intermediates in many chemical reactions; hence, considerable effort has gone into investigating their structures and properties, for example, in superacids, in salts, or in the gas phase. However, studies of the vibrational structure of carbocations are not abundant, because their infrared spectra are difficult to obtain in superacids or salts (where furthermore the cations may be perturbed by counterions), and the generation of gas-phase carbocations in discharges u...

  18. Cationic dialkylarylphosphates: a new family of bio-inspired cationic lipids for gene delivery. (United States)

    Le Corre, Stéphanie S; Belmadi, Nawal; Berchel, Mathieu; Le Gall, Tony; Haelters, Jean-Pierre; Lehn, Pierre; Montier, Tristan; Jaffrès, Paul-Alain


    In this work that aims to synthesize and evaluate new cationic lipids as vectors for gene delivery, we report the synthesis of a series of cationic lipids in which a phosphate functional group acts as a linker to assemble on a molecular scale, two lipid chains and one cationic polar head. The mono or dicationic moiety is connected to the phosphate group by an aryl spacer. In this work, two synthesis strategies were evaluated. The first used the Atherton-Todd coupling reaction to introduce a phenolic derivative to dioleylphosphite. The second strategy used a sequential addition of lipid alcohol and a phenolic derivative on POCl3. The two methods are efficient, but the latter allows larger yields. Different polar head groups were introduced, thus producing amphiphilic compounds possessing either one permanent (N-methyl-imidazolium, pyridinium, trimethylammonium) or two permanent cationic charges. All these cationic lipids were formulated as liposomal solutions and characterized (size and zeta potential). They formed stable liposomal solutions both in water (at pH 7.0) and in a weakly acidic medium (at pH 5.5). Finally, this new generation of cationic lipids was used to deliver DNA into various human-derived epithelial cells cultured in vitro. Compared with Lipofectamine used as a reference commercial lipofection reagent, some cationic dialkylarylphosphates were able to demonstrate potent gene transfer abilities, and noteworthily, monocationic derivatives were much more efficient than dicationic analogues.

  19. Mechanistic information on the reductive elimination from cationic trimethylplatinum(IV) complexes to form carbon-carbon bonds. (United States)

    Procelewska, Joanna; Zahl, Achim; Liehr, Günter; van Eldik, Rudi; Smythe, Nicole A; Williams, B Scott; Goldberg, Karen I


    Cationic complexes of the type fac-[(L(2))Pt(IV)Me(3)(pyr-X)][OTf] (pyr-X = 4-substituted pyridines; L(2) = diphosphine, viz., dppe = bis(diphenylphosphino)ethane and dppbz = o-bis(diphenylphosphino)benzene; OTf = trifluoromethanesulfonate) undergo C-C reductive elimination reactions to form [L(2)Pt(II)Me(pyr-X)][OTf] and ethane. Detailed studies indicate that these reactions proceed by a two-step pathway, viz., initial reversible dissociation of the pyridine ligand from the cationic complex to generate a five-coordinate Pt(IV) intermediate, followed by irreversible concerted C-C bond formation. The reaction is inhibited by pyridine. The highly positive values for DeltaS()(obs) = +180 +/- 30 J K(-1) mol(-1), DeltaH(obs) = 160 +/- 10 kJ mol(-1), and DeltaV()(obs) = +16 +/- 1 cm(3) mol(-1) can be accounted for in terms of significant bond cleavage and/or partial reduction from Pt(IV) to Pt(II) in going from the ground to the transition state. These cationic complexes have provided the first opportunity to carry out detailed studies of C-C reductive elimination from cationic Pt(IV) complexes in a variety of solvents. The absence of a significant solvent effect for this reaction provides strong evidence that the C-C reductive coupling occurs from an unsaturated five-coordinate Pt(IV) intermediate rather than from a six-coordinate Pt(IV) solvento species.

  20. Solution-phase mechanistic study and solid-state structure of a tris(bipyridinium radical cation) inclusion complex. (United States)

    Fahrenbach, Albert C; Barnes, Jonathan C; Lanfranchi, Don Antoine; Li, Hao; Coskun, Ali; Gassensmith, Jeremiah J; Liu, Zhichang; Benítez, Diego; Trabolsi, Ali; Goddard, William A; Elhabiri, Mourad; Stoddart, J Fraser


    The ability of the diradical dicationic cyclobis(paraquat-p-phenylene) (CBPQT(2(•+))) ring to form inclusion complexes with 1,1'-dialkyl-4,4'-bipyridinium radical cationic (BIPY(•+)) guests has been investigated mechanistically and quantitatively. Two BIPY(•+) radical cations, methyl viologen (MV(•+)) and a dibutynyl derivative (V(•+)), were investigated as guests for the CBPQT(2(•+)) ring. Both guests form trisradical complexes, namely, CBPQT(2(•+))⊂MV(•+) and CBPQT(2(•+))⊂V(•+), respectively. The structural details of the CBPQT(2(•+))⊂MV(•+) complex, which were ascertained by single-crystal X-ray crystallography, reveal that MV(•+) is located inside the cavity of the ring in a centrosymmetric fashion: the 1:1 complexes pack in continuous radical cation stacks. A similar solid-state packing was observed in the case of CBPQT(2(•+)) by itself. Quantum mechanical calculations agree well with the superstructure revealed by X-ray crystallography for CBPQT(2(•+))⊂MV(•+) and further suggest an electronic asymmetry in the SOMO caused by radical-pairing interactions. The electronic asymmetry is maintained in solution. The thermodynamic stability of the CBPQT(2(•+))⊂MV(•+) complex was probed by both isothermal titration calorimetry (ITC) and UV/vis spectroscopy, leading to binding constants of (5.0 ± 0.6) × 10(4) M(-1) and (7.9 ± 5.5) × 10(4) M(-1), respectively. The kinetics of association and dissociation were determined by stopped-flow spectroscopy, yielding a k(f) and k(b) of (2.1 ± 0.3) × 10(6) M(-1) s(-1) and 250 ± 50 s(-1), respectively. The electrochemical mechanistic details were studied by variable scan rate cyclic voltammetry (CV), and the experimental data were compared digitally with simulated data, modeled on the proposed mechanism using the thermodynamic and kinetic parameters obtained from ITC, UV/vis, and stopped-flow spectroscopy. In particular, the electrochemical mechanism of association

  1. Effects of intermediate load on performance limitations in excitation control

    Directory of Open Access Journals (Sweden)

    Pichai Aree


    Full Text Available The stability of excitation control systems is of great concern in power system operations. In this paper, the effects of intermediate load on performance limitation in excitation control are studied. The results reveal that the open-loop characteristic of synchronous machine’s flux linkage can be changed from minimum to non-minimum phase at a high level of intermediate load. This change leads to instability of synchronous machines under manual excitation control. A particular emphasis is also given to investigate the fundamental limitations in excitation control, imposed by non-minimum phases with regard to the open-loop right-half-plane (ORHP pole. The study demonstrates the difficulties of excitation control tuning to achieve the desired performance and robustness under the ORHP pole occurrence. Moreover, this paper shows the conditional stability in excitation control loop, where either an increase or decrease of the exciter gain causes a destabilization of the system’s stability. Frequency response techniques are used for these investigations.

  2. Cation Selectivity in Biological Cation Channels Using Experimental Structural Information and Statistical Mechanical Simulation. (United States)

    Finnerty, Justin John; Peyser, Alexander; Carloni, Paolo


    Cation selective channels constitute the gate for ion currents through the cell membrane. Here we present an improved statistical mechanical model based on atomistic structural information, cation hydration state and without tuned parameters that reproduces the selectivity of biological Na+ and Ca2+ ion channels. The importance of the inclusion of step-wise cation hydration in these results confirms the essential role partial dehydration plays in the bacterial Na+ channels. The model, proven reliable against experimental data, could be straightforwardly used for designing Na+ and Ca2+ selective nanopores.

  3. Mixed cation effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.

    , network structure, and the resistances associated with the deformation processes in mixed cation glasses by partially substituting magnesium for calcium and calcium for lithium in sodium aluminosilicate glasses. We use Raman and 27Al NMR spectroscopies to obtain insights into the structural...

  4. Resonance raman studies of phenylcyclopropane radical cations

    NARCIS (Netherlands)

    Godbout, J.T.; Zuilhof, H.; Heim, G.; Gould, I.R.; Goodman, J.L.; Dinnocenzo, J.P.; Myers Kelley, A.


    Resonance Raman spectra of the radical cations of phenylcyclopropane and trans-1-phenyl-2-methylcyclopropane are reported. A near-UV pump pulse excites a photosensitizer which oxidizes the species of interest, and a visible probe pulse delayed by 35 ns obtains the spectrum of the radical ion. The tr

  5. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.;


    Polypyrrole (PPy) polymer films permanently doped with large, immobile anion dodecyl benzene sulfonate (DBS) have been characterized by cyclic voltammetry in order to clarify the roles of cations and anions in the aqueous electrolyte as mobile ions in the film. Aqueous solutions of 0.05-0.1 M...... alkali metal chlorides as well as BaCl2, NaBr and (CH3CH2CH2)(4)NBr were used to investigate the effects of both the ionic charge, size and shape. In 1: 1 electrolytes using small ions only three peaks are present: a sharp cathodic peak at ca. - 0.6 V vs, SCE representing both the insertion of cations...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  6. Anionic/cationic complexes in hair care. (United States)

    O'Lenick, Tony


    The formulation of cosmetic products is always more complicated than studying the individual components in aqueous solution. This is because there are numerous interactions between the components, which make the formulation truly more than the sum of the parts. This article will look at interactions between anionic and cationic surfactants and offer insights into how to use these interactions advantageously in making formulations.

  7. Controlled Cationic Polymerization of N-Vinylcarbazol

    NARCIS (Netherlands)

    Nuyken, O.; Rieß, G.; Loontjens, J.A.


    Cationic polymerization of N-Vinylcarbazol (NVC) was initiated with 1-iodo-1-(2-methylpropyloxy)ethane in the presence of N(n-Bu)4ClO4 and without addition of this activator. Furthermore, 1-chloro-1-(2-methylpropyloxy) ethane, with and without activator has been applied as initiator for NVC. These i

  8. Dendritic Cells Stimulated by Cationic Liposomes. (United States)

    Vitor, Micaela Tamara; Bergami-Santos, Patrícia Cruz; Cruz, Karen Steponavicius Piedade; Pinho, Mariana Pereira; Barbuto, José Alexandre Marzagão; De La Torre, Lucimara Gaziola


    Immunotherapy of cancer aims to harness the immune system to detect and destroy cancer cells. To induce an immune response against cancer, activated dendritic cells (DCs) must present tumor antigens to T lymphocytes of patients. However, cancer patients' DCs are frequently defective, therefore, they are prone to induce rather tolerance than immune responses. In this context, loading tumor antigens into DCs and, at the same time, activating these cells, is a tempting goal within the field. Thus, we investigated the effects of cationic liposomes on the DCs differentiation/maturation, evaluating their surface phenotype and ability to stimulate T lymphocytes proliferation in vitro. The cationic liposomes composed by egg phosphatidylcholine, 1,2-dioleoyl-3-trimethylammonium propane and 1,2-dioleoylphosphatidylethanolamine (50/25/25% molar) were prepared by the thin film method followed by extrusion (65 nm, polydispersity of 0.13) and by the dehydration-rehydration method (95% of the population 107 nm, polydispersity of 0.52). The phenotypic analysis of dendritic cells and the analysis of T lymphocyte proliferation were performed by flow cytometry and showed that both cationic liposomes were incorporated and activated dendritic cells. Extruded liposomes were better incorporated and induced higher CD86 expression for dendritic cells than dehydrated-rehydrated vesicles. Furthermore, dendritic cells which internalized extruded liposomes also provided stronger T lymphocyte stimulation. Thus, cationic liposomes with a smaller size and polydispersity seem to be better incorporated by dendritic cells. Hence, these cationic liposomes could be used as a potential tool in further cancer immunotherapy strategies and contribute to new strategies in immunotherapy.

  9. Evidence of interlipidic ion-pairing in anion-induced DNA release from cationic amphiphile-DNA complexes. Mechanistic implications in transfection. (United States)

    Bhattacharya, S; Mandal, S S


    Complex formation of DNA with a number of cationic amphiphiles has been examined using fluorescence, gel electrophoresis, and chemical nuclease digestion. Here we have addressed the status of both DNA and lipid upon complexation with each other. DNA upon binding with cationic amphiphiles changes its structure in such a way that it loses the ability to intercalate and becomes resistant to nuclease digestion. Fluorescence anisotropy measurements due to 1, 6-diphenylhexatriene (DPH) doped in cationic liposomes demonstrated that upon complexation with DNA, the resulting complexes still retain lamellar organizations with modest enhancement in thermal stabilities. The lipid-DNA complexation is most effective only when the complexation was carried out at or around the phase transition temperatures of the cationic lipid employed in the complexation with DNA. The release of DNA from cationic lipid-DNA complexes could be induced by several anionic additives. Determination of fluorescence anisotropies (due to DPH) as a function of temperature clearly demonstrates that the addition of equivalent amounts of anionic amphiphile into cationic lipid-DNA complexes leads to the ion-pairing of the amphiphiles, the melting profiles of which are virtually the same as those obtained in the absence of DNA. In this process DNA gets released from its complexes with cationic lipids and regains its natural intercalation ability, movement, and staining ability on agarose gel and also the sensitivities toward nuclease digestion. This clearly suggests that combination of ion-pairing and hydrophobic interactions between cationic and anionic amphiphiles is stronger than the electrostatic forces involved in the cationic lipid-DNA complexation. It is further revealed that the DNA release by anions is most efficient from the cationic lipid-DNA complexes at or around the Tm of the cationic lipid used in DNA complexation. This explains why more effective DNA delivery is achieved with cationic lipids

  10. A New Vaccinia Virus Intermediate Transcription Factor


    Sanz, Patrick; Moss, Bernard


    Transcription of the vaccinia virus genome is mediated by a virus-encoded multisubunit DNA-dependent RNA polymerase in conjunction with early-, intermediate-, and late-stage-specific factors. Previous studies indicated that two virus-encoded proteins (capping enzyme and VITF-1) and one unidentified cellular protein (VITF-2) are required for specific transcription of an intermediate promoter template in vitro. We have now extensively purified an additional virus-induced intermediate transcript...

  11. Organic Cations Might Not Be Essential to the Remarkable Properties of Band Edge Carriers in Lead Halide Perovskites. (United States)

    Zhu, Haiming; Trinh, M Tuan; Wang, Jue; Fu, Yongping; Joshi, Prakriti P; Miyata, Kiyoshi; Jin, Song; Zhu, X-Y


    A charge carrier in a lead halide perovskite lattice is protected as a large polaron responsible for the remarkable photophysical properties, irrespective of the cation type. All-inorganic-based APbX3 perovskites may mitigate the stability problem for their applications in solar cells and other optoelectronics.

  12. Experiments in intermediate energy physics

    Energy Technology Data Exchange (ETDEWEB)

    Dehnhard, D.


    Research in experimental nuclear physics was done from 1979 to 2002 primarily at intermediate energy facilities that provide pion, proton, and kaon beams. Particularly successful has been the work at the Los Alamos Meson Physics Facility (LAMPF) on unraveling the neutron and proton contributions to nuclear ground state and transition densities. This work was done on a wide variety of nuclei and with great detail on the carbon, oxygen, and helium isotopes. Some of the investigations involved the use of polarized targets which allowed the extraction of information on the spin-dependent part of the triangle-nucleon interaction. At the Indiana University Cyclotron Facility (IUCF) we studied proton-induced charge exchange reactions with results of importance to astrophysics and the nuclear few-body problem. During the first few years, the analysis of heavy-ion nucleus scattering data that had been taken prior to 1979 was completed. During the last few years we created hypernuclei by use of a kaon beam at Brookhaven National Laboratory (BNL) and an electron beam at Jefferson Laboratory (JLab). The data taken at BNL for a study of the non-mesonic weak decay of the A particle in a nucleus are still under analysis by our collaborators. The work at JLab resulted in the best resolution hypernuclear spectra measured thus far with magnetic spectrometers.

  13. Dipicolinate complexes of main group metals with hydrazinium cation

    Indian Academy of Sciences (India)

    K Saravanan; S Govindarajan


    Some new coordination complexes of hydrazinium main group metal dipicolinate hydrates of formulae (N2H5)2M(dip)2.H2O (where, M =Ca, Sr, Ba or Pb and = 0, 2, 4 and 3 respectively and dip = dipicolinate), N2H5Bi(dip)2.3H2O and (N2H5)3Bi(dip)3.4H2O have been prepared and characterized by physico-chemical techniques. The infrared spectra of the complexes reveal the presence of tridentate dipicolinate dianions and non-coordinating hydrazinium cations. Conductance measurements show that the mono, di and trihydrazinium complexes behave as 1:1, 2:1 and 3:1 electrolytes respectively, in aqueous solution. Thermal decomposition studies show that these compounds lose water followed by endothermic decomposition of hydrazine to give respective metal hydrogendipicolinate intermediates, which further decompose exothermically to the final product of either metal carbonates (Ca, Sr, Ba and Pb) or metal oxycarbonates (Bi). The coordination numbers around the metal ions differ from compound to compound. The various coordination numbers exhibited by these metals are six (Ca), seven (Ba), eight (Sr) and nine (Pb and Bi). In all the complexes the above coordination number is attained by tridentate dipicolinate dianions and water molecules. The X-ray diffraction patterns of these compounds differ from one another suggesting that they are not isomorphous.

  14. Metal Phosphates as Intermediate Temperature Proton Conducting Electrolytes

    DEFF Research Database (Denmark)

    Huang, Yunjie; Li, Q.F.; Pan, Chao


    A series of metal phosphates were synthesized and screened as potential proton conductor electrolytes for fuel cells and electrolysers operational at intermediate temperatures. Among the selected, niobium and bismuth phosphates exhibited a proton conductivity of 10-2 and 10-7 S cm-1, respectively......, under the anhydrous atmosphere at 250 °C, showing close correlation with the presence of hydroxyl groups in the phosphate phases. At the water partial pressure of above 0.6 atm, both phosphates possessed a proton conductivity to a level of above 3 x 10-2 S cm-1. Reasonable stability of the proton...

  15. Multiple unfolding intermediates of human placental alkaline phosphatase in equilibrium urea denaturation. (United States)

    Hung, H C; Chang, G G


    Alkaline phosphatase is an enzyme with a typical alpha/beta hydrolase fold. The conformational stability of the human placental alkaline phosphatase was examined with the chemical denaturant urea. The red shifts of fluorescence spectra show a complex unfolding process involving multiple equilibrium intermediates indicating differential stability of the subdomains of the enzyme. None of these unfolding intermediates were observed in the presence of 83 mM NaCl, indicating the importance of ionic interactions in the stabilization of the unfolding intermediates. Guanidinium chloride, on the other hand, could stabilize one of the unfolding intermediates, which is not a salt effect. Some of the unfolding intermediates were also observed in circular dichroism spectroscopy, which clearly indicates steady loss of helical structure during unfolding, but very little change was observed for the beta strand content until the late stage of the unfolding process. The enzyme does not lose its phosphate-binding ability after substantial tertiary structure changes, suggesting that the substrate-binding region is more resistant to chemical denaturant than the other structural domains. Global analysis of the fluorescence spectral change demonstrated the following folding-unfolding process of the enzyme: N I(1) I(2) I(3) I(4) I(5) D. These discrete intermediates are stable at urea concentrations of 2.6, 4.1, 4.7, 5.5, 6.6, and 7.7 M, respectively. These intermediates are further characterized by acrylamide and/or potassium iodide quenching of the intrinsic fluorescence of the enzyme and by the hydrophobic probes, 1-anilinonaphthalene-8-sulfonic acid and 4,4'-dianilino-1,1'-binaphthyl-5,5'-disulfonic acid. The stepwise unfolding process was interpreted by the folding energy landscape in terms of the unique structure of the enzyme. The rigid central beta-strand domain is surrounded by the peripheral alpha-helical and coil structures, which are marginally stable toward a chemical

  16. Spectroscopic detection, reactivity, and acid-base behavior of ring-dimethoxylated phenylethanoic acid radical cations and radical zwitterions in aqueous solution. (United States)

    Bietti, Massimo; Capone, Alberto


    A product and time-resolved kinetic study of the one-electron oxidation of ring-dimethoxylated phenylethanoic acids has been carried out at different pH values. Oxidation leads to the formation of aromatic radical cations or radical zwitterions depending on pH, and pK(a) values for the corresponding acid-base equilibria have been measured. The radical cations undergo decarboxylation with first-order rate constants (k(dec)) ranging from <10(2) to 5.6 x 10(4) s(-1) depending on radical cation stability. A significant increase in k(dec) (between 10 and 40 times) is observed on going from the radical cations to the corresponding radical zwitterions. The results are discussed in terms of the ease of intramolecular side chain to ring electron transfer required for decarboxylation, in both the radical cations and radical zwitterions.

  17. Ideal Stabilization

    CERN Document Server

    Nesterenko, Mikhail


    We define and explore the concept of ideal stabilization. The program is ideally stabilizing if its every state is legitimate. Ideal stabilization allows the specification designer to prescribe with arbitrary degree of precision not only the fault-free program behavior but also its recovery operation. Specifications may or may not mention all possible states. We identify approaches to designing ideal stabilization to both kinds of specifications. For the first kind, we state the necessary condition for an ideally stabilizing solution. On the basis of this condition we prove that there is no ideally stabilizing solution to the leader election problem. We illustrate the utility of the concept by providing examples of well-known programs and proving them ideally stabilizing. Specifically, we prove ideal stabilization of the conflict manager, the alternator, the propagation of information with feedback and the alternating bit protocol.

  18. Cu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange

    KAUST Repository

    Casu, Alberto


    Among the different synthesis approaches to colloidal nanocrystals a recently developed toolkit is represented by cation exchange reactions, where the use of template nanocrystals gives access to materials that would be hardly attainable via direct synthesis. Besides, post-synthetic treatments, such as thermally activated solid state reactions, represent a further flourishing route to promote finely controlled cation exchange. Here, we report that, upon in situ heating in a transmission electron microscope, Cu2Se nanocrystals deposited on an amorphous solid substrate undergo partial loss of Cu atoms, which are then engaged in local cation exchange reactions with Cu “acceptors” phases represented by rod- and wire- shaped CdSe nanocrystals. This thermal treatment slowly transforms the initial CdSe nanocrystals into Cu2-xSe nanocrystals, through the complete sublimation of Cd and the partial sublimation of Se atoms. Both Cu “donor” and “acceptor” particles were not always in direct contact with each other, hence the gradual transfer of Cu species from Cu2Se or metallic Cu to CdSe nanocrystals was mediated by the substrate and depended on the distance between the donor and acceptor nanostructures. Differently from what happens in the comparably faster cation exchange reactions performed in liquid solution, this study shows that slow cation exchange reactions can be performed at the solid state, and helps to shed light on the intermediate steps involved in such reactions.

  19. Cd/Hg cationic substitution in magic-sized CdSe clusters: Optical characterization and theoretical studies

    Energy Technology Data Exchange (ETDEWEB)

    Antanovich, Artsiom; Prudnikau, Anatol; Gurin, Valerij; Artemyev, Mikhail, E-mail:


    Highlights: • HgSe magic-sized clusters were prepared via Cd/Hg cationic exchange in pyridine. • Upon cationic exchange CdSe clusters behave differently from quantum dots or rods. • Theoretical calculations of magic-sized clusters agree well with experimental data. - Abstract: We examine conversion of magic-sized CdSe clusters (MSCs) into HgSe ones by means of Cd/Hg cation exchange. With this procedure Cd{sub 8}Cd{sub 17}– and Cd{sub 32}–selenide clusters can be converted into corresponding Hg{sub 8}–, Hg{sub 17}– and Hg{sub 32}–selenide ones. Upon cationic exchange MSCs behavior differs from that of bulkier counterparts – larger (2–3 nm) quantum dots. Unlike CdSe colloidal quantum dots, magic-sized clusters are converted in fast and complete manner without a formation of intermediate mixed Cd{sub x}Hg{sub 1−x} compounds that was established on the basis of optical absorption spectroscopy and chemical composition analysis. These assumptions were supported by DFT quantum chemical calculations performed for Cd{sub 8}–, Cd{sub 17}– and Hg{sub 8}–, Hg{sub 17}–selenide model clusters. Energies of experimental and calculated optical transitions were compared in order to prove the isostructural character of cationic substitution in magic-sized clusters.

  20. Preparation and Characterization of Cationic PLA-PEG Nanoparticles for Delivery of Plasmid DNA

    Directory of Open Access Journals (Sweden)

    Zou Weiwei


    Full Text Available Abstract The purpose of the present work was to formulate and evaluate cationic poly(lactic acid-poly(ethylene glycol (PLA-PEG nanoparticles as novel non-viral gene delivery nano-device. Cationic PLA-PEG nanoparticles were prepared by nanoprecipitation method. The gene loaded nanoparticles were obtained by incubating the report gene pEGFP with cationic PLA-PEG nanoparticles. The physicochemical properties (e.g., morphology, particle size, surface charge, DNA binding efficiency and biological properties (e.g., integrity of the released DNA, protection from nuclease degradation, plasma stability, in vitro cytotoxicity, and in vitro transfection ability in Hela cells of the gene loaded PLA-PEG nanoparticles were evaluated, respectively. The obtained cationic PLA-PEG nanoparticles and gene loaded nanoparticles were both spherical in shape with average particle size of 89.7 and 128.9 nm, polydispersity index of 0.185 and 0.161, zeta potentials of +28.9 and +16.8 mV, respectively. The obtained cationic PLA-PEG nanoparticles with high binding efficiency (>95% could protect the loaded DNA from the degradation by nuclease and plasma. The nanoparticles displayed sustained-release properties in vitro and the released DNA maintained its structural and functional integrity. It also showed lower cytotoxicity than Lipofectamine 2000 and could successfully transfect gene into Hela cells even in presence of serum. It could be concluded that the established gene loaded cationic PLA-PEG nanoparticles with excellent properties were promising non-viral nano-device, which had potential to make cancer gene therapy achievable.

  1. Preparation and Characterization of Cationic PLA-PEG Nanoparticles for Delivery of Plasmid DNA (United States)

    Zou, Weiwei; Liu, Chunxi; Chen, Zhijin; Zhang, Na


    The purpose of the present work was to formulate and evaluate cationic poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) nanoparticles as novel non-viral gene delivery nano-device. Cationic PLA-PEG nanoparticles were prepared by nanoprecipitation method. The gene loaded nanoparticles were obtained by incubating the report gene pEGFP with cationic PLA-PEG nanoparticles. The physicochemical properties (e.g., morphology, particle size, surface charge, DNA binding efficiency) and biological properties (e.g., integrity of the released DNA, protection from nuclease degradation, plasma stability, in vitro cytotoxicity, and in vitro transfection ability in Hela cells) of the gene loaded PLA-PEG nanoparticles were evaluated, respectively. The obtained cationic PLA-PEG nanoparticles and gene loaded nanoparticles were both spherical in shape with average particle size of 89.7 and 128.9 nm, polydispersity index of 0.185 and 0.161, zeta potentials of +28.9 and +16.8 mV, respectively. The obtained cationic PLA-PEG nanoparticles with high binding efficiency (>95%) could protect the loaded DNA from the degradation by nuclease and plasma. The nanoparticles displayed sustained-release properties in vitro and the released DNA maintained its structural and functional integrity. It also showed lower cytotoxicity than Lipofectamine 2000 and could successfully transfect gene into Hela cells even in presence of serum. It could be concluded that the established gene loaded cationic PLA-PEG nanoparticles with excellent properties were promising non-viral nano-device, which had potential to make cancer gene therapy achievable.

  2. Bithiophene radical cation: Resonance Raman spectroscopy and molecular orbital calculations

    DEFF Research Database (Denmark)

    Grage, M.M.-L.; Keszthelyi, T.; Offersgaard, J.F.


    The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution a...


    Institute of Scientific and Technical Information of China (English)

    Dongmei Yu; Chuanshan Zhao; Kefu Chen


    This study investigated the effects of several different cationic additives on the viscosity 、zeta potential and printing properties of the ink-jet coating. The cationic additives have greatly improved sheet's gloss and printabilities.

  4. Ion dynamics in cationic lipid bilayer systems in saline solutions

    DEFF Research Database (Denmark)

    Miettinen, Markus S; Gurtovenko, Andrey A; Vattulainen, Ilpo


    mixture of cationic dimyristoyltrimethylammoniumpropane (DMTAP) and zwitterionic (neutral) dimyristoylphosphatidylcholine (DMPC) lipids. Using atomistic molecular dynamics simulations, we address the effects of bilayer composition (cationic to zwitterionic lipid fraction) and of NaCl electrolyte...

  5. Radical-cationic gaseous amino acids: a theoretical study. (United States)

    Sutherland, Kailee N; Mineau, Philippe C; Orlova, Galina


    Three major forms of gaseous radical-cationic amino acids (RCAAs), keto (COOH), enolic (C(OH)OH), and zwitterionic (COO(-)), as well as their tautomers, are examined for aliphatic Ala(.+), Pro(.+), and Ser(.+), sulfur-containing Cys(.+), aromatic Trp(.+), Tyr(.+), and Phe(.+), and basic His(.+). The hybrid B3LYP exchange-correlation functional with various basis sets along with the highly correlated CCSD(T) method is used. For all RCAAs considered, the main stabilizing factor is spin delocalization; for His(.+), protonation of the basic side chain is equally important. Minor stabilizing factors are hydrogen bonding and 3e-2c interactions. An efficient spin delocalization along the N-C(alpha)-C(O-)O moiety occurs upon H-transfer from C(alpha) to the carboxylic group to yield the captodative enolic form, which is the lowest-energy isomer for Ala(.+), Pro(.+), Ser(.+), Cys(.+), Tyr(.+), and Phe(.+). This H-transfer occurs in a single step as a 1,3-shift through the sigma-system. For His(.+), the lowest-energy isomer is formed upon H-transfer from C(alpha) to the basic side chain, which results in a keto form, with spin delocalized along the N-C(alpha)-C=O fragment. Trp(.+) is the only RCAA that favors spin delocalization over an aromatic system given the low ionization energy of indole. The lowest-energy isomer of Trp(.+) is a keto form, with no H-transfer.

  6. Electrolytes For Intermediate Temperature Solid Oxide Fuel Cells

    Directory of Open Access Journals (Sweden)

    Rękas M.


    Full Text Available Solid electrolytes for construction of the intermediate-temperature solid oxide fuel cells, IT-SOFC, have been reviewed. Yttrium stabilized tetragonal zirconia polycrystals, YTZP, as a potential electrolyte of IT-SOFC have been highlighted. The experimental results involving structural, microstructural, electrical properties based on our own studies were presented. In order to study aluminum diffusion in YTZP, aluminum oxide was deposited on the surface of 3 mol.% yttria stabilized tetragonal zirconia polycrystals (3Y-TZP. The samples were annealed at temperatures from 1523 to 1773 K. Diffusion profiles of Al in the form of mean concentration vs. depth in B-type kinetic region were investigated by secondary ion mass spectroscopy (SIMS. Both the lattice (DB and grain boundary (DGB diffusion were determined.

  7. Electron transfer-induced four-membered cyclic intermediate formation: Olefin cross-coupling vs. olefin cross-metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Okada, Yohei [Department of Applied Life Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509 (Japan); Chiba, Kazuhiro, E-mail: [Department of Applied Life Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509 (Japan)


    An electron transfer-induced four-membered cyclic intermediate, formed between a radical cation of an enol ether and an unactivated olefin, played a key role in the pathway toward either cross-coupling or cross-metathesis. The presence of an alkoxy group on the phenyl ring of the olefin entirely determined the synthetic outcome of the reaction, which mirrored the efficiency of the intramolecular electron transfer.

  8. Air Conditioning. Performance Objectives. Intermediate Course. (United States)

    Long, William

    Several intermediate performance objectives and corresponding criterion measures are listed for each of seven terminal objectives for an intermediate air conditioning course. The titles of the seven terminal objectives are Refrigeration Cycle, Job Requirement Skills, Air Conditioning, Trouble Shooting, Performance Test, Shop Management, and S.I.E.…

  9. Some Intermediate-Level Violin Concertos. (United States)

    Abramson, Michael


    Contends that many violin students attempt difficult concertos before they are technically or musically prepared. Identifies a variety of concertos at the intermediate and advanced intermediate-level for students to study and master before attempting the advanced works by Bach and Mozart. Includes concertos by Vivaldi, Leclair, Viotti, Haydn,…

  10. 19 CFR 122.84 - Intermediate airport. (United States)


    ... 19 Customs Duties 1 2010-04-01 2010-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the:...

  11. Cation Permeability in Soybean Aleurone Layer


    Noda, Hiroko; Fukuda, Mitsuru


    The permeation of water and ions into bean seeds is essential for processing and cooking of beans. The permeability of cations, K, Na, Ca, and Mg ions, into soybean seed tissue, especially aleurone layer, during water uptake was investigated to characterize the ion permeation into soybeans. Aleurone layers and seed coats contained relatively high concentration of endogenous K and Ca ions, and endogenous Ca ion, respectively. The amounts of Ca ion entered seed coats and aleurone layers were gr...

  12. Aqueous complexation of trivalent lanthanide and actinide cations by N,N,N'{sub 2},N'-tetrakis(2-pyridylmethyl)ethylenediamine.

    Energy Technology Data Exchange (ETDEWEB)

    Beitz, J. V.; Ensor, D. D.; Jensen, M. P.; Morss, L. R.


    The aqueous complexation reactions of trivalent lanthanide and actinide cations with the hexadentate ligand N,N,N{prime},N{prime}-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN), have been characterized using potentiometric and spectroscopic techniques in 0.1 M NaClO{sub 4} At 25 C, the stability constant of Am(TPEN){sup 3+} is two orders of magnitude larger than that of Sm(TPEN){sup 3+}, reflecting the stronger interactions of the trivalent actinide cations with softer ligands as compared to lanthanide cations.

  13. Limited data speaker identification

    Indian Academy of Sciences (India)

    H S Jayanna; S R Mahadeva Prasanna


    In this paper, the task of identifying the speaker using limited training and testing data is addressed. Speaker identification system is viewed as four stages namely, analysis, feature extraction, modelling and testing. The speaker identification performance depends on the techniques employed in these stages. As demonstrated by different experiments, in case of limited training and testing data condition, owing to less data, existing techniques in each stage will not provide good performance. This work demonstrates the following: multiple frame size and rate (MFSR) analysis provides improvement in the analysis stage, combination of mel frequency cepstral coefficients (MFCC), its temporal derivatives $(\\Delta,\\Delta \\Delta)$, linear prediction residual (LPR) and linear prediction residual phase (LPRP) features provides improvement in the feature extraction stage and combination of learning vector quantization (LVQ) and gaussian mixture model – universal background model (GMM–UBM) provides improvement in the modelling stage. The performance is further improved by integrating the proposed techniques at the respective stages and combining the evidences from them at the testing stage. To achieve this, we propose strength voting (SV), weighted borda count (WBC) and supporting systems (SS) as combining methods at the abstract, rank and measurement levels, respectively. Finally, the proposed hierarchical combination (HC) method integrating these three methods provides significant improvement in the performance. Based on these explorations, this work proposes a scheme for speaker identification under limited training and testing data.

  14. Controlling chemistry with cations: photochemistry within zeolites. (United States)

    Ramamurthy, V; Shailaja, J; Kaanumalle, Lakshmi S; Sunoj, R B; Chandrasekhar, J


    The alkali ions present in the supercages of zeolites X and Y interact with included guest molecules through quadrupolar (cation-pi), and dipolar (cation-carbonyl) interactions. The presence of such interactions can be inferred through solid-state NMR spectra of the guest molecules. Alkali ions, as illustrated in this article, can be exploited to control the photochemical and photophysical behaviors of the guest molecules. For example, molecules that rarely phosphoresce can be induced to do so within heavy cation-exchanged zeolites. The nature (electronic configuration) of the lowest triplet state of carbonyl compounds can be altered with the help of light alkali metal ions. This state switch (n pi*-pi pi*) helps to bring out reactivity that normally remains dormant. Selectivity obtained during the singlet oxygen oxidation of olefins within zeolites illustrates the remarkable control that can be exerted on photoreactions with the help of a confined medium that also has active sites. The reaction cavities of zeolites, like enzymes, are not only well-defined and confined, but also have active sites that closely guide the reactant molecule from start to finish. The examples provided here illustrate that zeolites are far more useful than simple shape-selective catalysts.

  15. Computational and analytical modeling of cationic lipid-DNA complexes. (United States)

    Farago, Oded; Grønbech-Jensen, Niels


    We present a theoretical study of the physical properties of cationic lipid-DNA (CL-DNA) complexes--a promising synthetically based nonviral carrier of DNA for gene therapy. The study is based on a coarse-grained molecular model, which is used in Monte Carlo simulations of mesoscopically large systems over timescales long enough to address experimental reality. In the present work, we focus on the statistical-mechanical behavior of lamellar complexes, which in Monte Carlo simulations self-assemble spontaneously from a disordered random initial state. We measure the DNA-interaxial spacing, d(DNA), and the local cationic area charge density, sigma(M), for a wide range of values of the parameter (c) representing the fraction of cationic lipids. For weakly charged complexes (low values of (c)), we find that d(DNA) has a linear dependence on (c)(-1), which is in excellent agreement with x-ray diffraction experimental data. We also observe, in qualitative agreement with previous Poisson-Boltzmann calculations of the system, large fluctuations in the local area charge density with a pronounced minimum of sigma(M) halfway between adjacent DNA molecules. For highly-charged complexes (large (c)), we find moderate charge density fluctuations and observe deviations from linear dependence of d(DNA) on (c)(-1). This last result, together with other findings such as the decrease in the effective stretching modulus of the complex and the increased rate at which pores are formed in the complex membranes, are indicative of the gradual loss of mechanical stability of the complex, which occurs when (c) becomes large. We suggest that this may be the origin of the recently observed enhanced transfection efficiency of lamellar CL-DNA complexes at high charge densities, because the completion of the transfection process requires the disassembly of the complex and the release of the DNA into the cytoplasm. Some of the structural properties of the system are also predicted by a continuum

  16. Material synthesis and fabrication method development for intermediate temperature solid oxide fuel cells (United States)

    Ding, Hanping

    Solid oxide fuel cells (SOFCs) are operated in high temperature conditions (750-1000 °C). The high operating temperature in turn may lead to very complicated material degradation issues, significantly increasing the cost and reducing the durability of SOFC material systems. In order to widen material selections, reduce cost, and increase durability of SOFCs, there is a growing interest to develop intermediate temperature SOFCs (500-750 °C). However, lowering operating temperature will cause substantial increases of ohmic resistance of electrolyte and polarization resistance of electrodes. This dissertation aimed at developing high-performance intermediate-temperature SOFCs through the employment of a series of layered perovskite oxides as novel cathode materials to minimize the potential electrode polarization on oxygen reduction reaction resulting from the unique crystal structure. The high performance of such perovskites under lower temperatures lies in the fact that a simple cubic perovskite with randomly occupied A-sites transforming into a layered compound with ordered lanthanide and alkali-earth cations may reduce the oxygen bonding strength and provide disorder-free channels for oxygen ion migrations. In order to compromise the cell performance and chemical and mechanical stability, the substitution of Fe in B site was comprehensively investigated to explore the effects of Fe doping on the crystal structure, thermal and electrical properties, as well as electrochemical performance. Furthermore, a platinum nanowire network was successfully developed as an ultrathin electrochemically efficient current collector for SOFCs. The unique platinum network on cathode surface can connect the oxygen reduction reaction (ORR) sites at the nano-scale to the external circuit while being able to substantially avoid blocking the open pores of the cathode. The superior electrochemical performance was exhibited, including the highly reduced electrode polarization resistance

  17. Cationic Effect on the Electrochemical Characteristics of the Hydrothermally Grown Manganese Dioxide (United States)

    Vernardou, D.; Kazas, A.; Apostolopoulou, M.; Katsarakis, N.; Koudoumas, E.


    Hydrothermal growth of manganese dioxide (MnO2) nanostructures was carried out on indium tin dioxide glass substrates at 95°C for 24 h to study the effect of cations such as K+, Li+, and Na+ on their properties. It was observed that presence of cations affected the MnO2 phase and morphology: amorphous MnO2 (no cations) showed columnar-like structure, ɛ-MnO2 (K+) presented nanowires, α-MnO2 (Na+) was composed of agglomerates of spherical nanoparticles, while β-MnO2 (Li+) consisted of spherical aggregates of nanoparticles. The different electrochemical performance depending on the structure is expected to be useful for application in Li-ion batteries. As-grown ɛ-MnO2 exhibited lower charge resistance and higher ionic diffusion rate, providing the electrode with enhanced specific discharge capacity of 910 mAh g-1 and capacity retention of 98% after 500 scans. Hence, K+ can support tunnel structures and stabilize the structure compared with the smaller cations Na+ and Li+.

  18. Effect of Extra-Framework Cations of LTL Nanozeolites to Inhibit Oil Oxidation (United States)

    Tan, Kok-Hou; Cham, Hooi-Ying; Awala, Hussein; Ling, Tau Chuan; Mukti, Rino R.; Wong, Ka-Lun; Mintova, Svetlana; Ng, Eng-Poh


    Lubricant oils take significant part in current health and environmental considerations since they are an integral and indispensable component of modern technology. Antioxidants are probably the most important additives used in oils because oxidative deterioration plays a major role in oil degradation. Zeolite nanoparticles (NPs) have been proven as another option as green antioxidants in oil formulation. The anti-oxidative behavior of zeolite NPs is obvious; however, the phenomenon is still under investigation. Herein, a study of the effect of extra-framework cations stabilized on Linde Type L (LTL) zeolite NPs (ca. 20 nm) on inhibition of oxidation in palm oil-based lubricant oil is reported. Hydrophilic LTL zeolites with a Si/Al ratio of 3.2 containing four different inorganic cations (Li+, Na+, K+, Ca2+) were applied. The oxidation of the lubricant oil was followed by visual observation, colorimetry, fourier transform infrared (FTIR) spectroscopy, 1H NMR spectroscopy, total acid number (TAN), and rheology analyses. The effect of extra-framework cations to slow down the rate of oil oxidation and to control the viscosity of oil is demonstrated. The degradation rate of the lubricant oil samples is decreased considerably as the polarizability of cation is increased with the presence of zeolite NPs. More importantly, the microporous zeolite NPs have a great influence in halting the steps that lead to the polymerization of the oils and thus increasing the lifetime of oils.

  19. Liquid-like cationic sub-lattice in copper selenide clusters (United States)

    White, Sarah L.; Banerjee, Progna; Jain, Prashant K.


    Super-ionic solids, which exhibit ion mobilities as high as those in liquids or molten salts, have been employed as solid-state electrolytes in batteries, improved thermoelectrics and fast-ion conductors in super-capacitors and fuel cells. Fast-ion transport in many of these solids is supported by a disordered, `liquid-like' sub-lattice of cations mobile within a rigid anionic sub-lattice, often achieved at high temperatures or pressures via a phase transition. Here we show that ultrasmall clusters of copper selenide exhibit a disordered cationic sub-lattice under ambient conditions unlike larger nanocrystals, where Cu+ ions and vacancies form an ordered super-structure similar to the bulk solid. The clusters exhibit an unusual cationic sub-lattice arrangement wherein octahedral sites, which serve as bridges for cation migration, are stabilized by compressive strain. The room-temperature liquid-like nature of the Cu+ sub-lattice combined with the actively tunable plasmonic properties of the Cu2Se clusters make them suitable as fast electro-optic switches.

  20. The isolable cation radical of disilene: synthesis, characterization, and a reversible one-electron redox system. (United States)

    Inoue, Shigeyoshi; Ichinohe, Masaaki; Sekiguchi, Akira


    The highly twisted tetrakis(di-tert-butylmethylsilyl)disilene 1 was treated with Ph3C+.BAr4- (BAr4-: TPFPB = tetrakis(pentafluorophenyl)borate) in toluene, producing disilene cation radical 3 upon one-electron oxidation. Cation radical 3 was isolated in the form of its borate salt as extremely air- and moisture-sensitive red-brown crystals. The molecular structure of 3 was established by X-ray crystallography, which showed a highly twisted structure (twisting angle of 64.9 degrees) along the central Si-Si bond with a bond length of 2.307(2) A, which is 2.1% elongated relative to that of 1. The cation radical is stabilized by sigma-pi hyperconjugation by the four tBu2MeSi groups attached to the two central sp2-Si atoms. An electron paramagnetic resonance (EPR) study of the hyperfine coupling constants (hfcc) of the 29Si nuclei indicates delocalization of the spin over the central two Si atoms. A reversible one-electron redox system between disilene, cation radical, and anion radical is also reported.

  1. Amino acid preference against beta sheet through allowing backbone hydration enabled by the presence of cation

    CERN Document Server

    Sharley, John N


    It is known that steric blocking by peptide sidechains of hydrogen bonding, HB, between water and peptide groups, PGs, in beta sheets accords with an amino acid intrinsic beta sheet preference. The present observations with Quantum Molecular Dynamics, QMD, simulation with quantum mechanical treatment of every water molecule solvating a beta sheet that would be transient in nature suggest that this steric blocking is not applicable in a hydrophobic region unless a cation is present, so that the amino acid beta sheet preference due to this steric blocking is only effective in the presence of a cation. We observed backbone hydration in a polyalanine and to a lesser extent polyvaline alpha helix without a cation being present, but a cation could increase the strength of these HBs. Parallel beta sheets have a greater tendency than antiparallel beta sheets of equivalent small size to retain regular structure in solvated QMD, and a 4 strand 4 inter-PG HB chain parallel beta sheet was used. Stability was reinforced b...

  2. Interaction of cationic dye/surfactants with Klebsiella K18 capsular polysaccharides: Physico-chemical studies

    Energy Technology Data Exchange (ETDEWEB)

    Nath, Ranendu Kumar, E-mail: [Department of Chemistry, Tripura University, Suryamaninagar, Tripura-799130 (India); Singh, Th. Charanjit [Department of Chemistry, D.D.M. College, Khowai, Tripura-799 202 (India); Dasgupta, Satwati [Department of Chemistry, Tripura University, Suryamaninagar, Tripura-799130 (India); Mitra, Asish [Department of Chemistry, MBB College, Agartala, Tripura-799001 (India); Panda, Amiya Kumar [Department of Chemistry, University of North Bengal, P.O. North Bengal University, Dt: Darjeeling, West Bengal-734013 (India)


    Physico-chemical studies on the interaction of capsular polysaccharide (SPS) isolated from Klebsiella K18, with cationic dyes and surfactants have been reported. SPS is an integral component of gram-negative bacteria and having glucuronic acid as the potential anionic site, induced strong metachromasy (blue shift {approx} 110 nm) in the cationic dye pinacyanol chloride (PCYN). Reversal of metachromasy was observed upon addition of co-solvents which provides a qualitative measurement of stability and nature of metachromatic compound associated with PCYN-SPS interaction. Thermodynamic parameters such as association constant, changes in free energy, enthalpy and entropy of dye-polymer interaction, were evaluated which revealed the nature of interaction. Studies on fluorescence quenching of acridine orange (AO) was also performed. The interaction of SPS with cationic and cationic-non-ionic mixed surfactant systems have been studied by turbidimetry, spectrophotometry, spectrofluorometry and viscosity measurements. The studies could provide an understanding on the effects of the surfactants on binding with the polymer. The binding was found to be electrostatic in origin and also hydrophobic in nature to a certain extent.

  3. Misfit strain driven cation inter-diffusion across an epitaxial multiferroic thin film interface (United States)

    Sankara Rama Krishnan, P. S.; Morozovska, Anna N.; Eliseev, Eugene A.; Ramasse, Quentin M.; Kepaptsoglou, Demie; Liang, Wen-I.; Chu, Ying-Hao; Munroe, Paul; Nagarajan, V.


    Cation intermixing at functional oxide interfaces remains a highly controversial area directly relevant to interface-driven nanoelectronic device properties. Here, we systematically explore the cation intermixing in epitaxial (001) oriented multiferroic bismuth ferrite (BFO) grown on a (001) lanthanum aluminate (LAO) substrate. Aberration corrected dedicated scanning transmission electron microscopy and electron energy loss spectroscopy reveal that the interface is not chemically sharp, but with an intermixing of ˜2 nm. The driving force for this process is identified as misfit-driven elastic strain. Landau-Ginzburg-Devonshire-based phenomenological theory was combined with the Sheldon and Shenoy formula in order to understand the influence of boundary conditions and depolarizing fields arising from misfit strain between the LAO substrate and BFO film. The theory predicts the presence of a strong potential gradient at the interface, which decays on moving into the bulk of the film. This potential gradient is significant enough to drive the cation migration across the interface, thereby mitigating the misfit strain. Our results offer new insights on how chemical roughening at oxide interfaces can be effective in stabilizing the structural integrity of the interface without the need for misfit dislocations. These findings offer a general formalism for understanding cation intermixing at highly strained oxide interfaces that are used in nanoelectronic devices.

  4. Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study. (United States)

    Sepehr, Fatemeh; Paddison, Stephen J


    Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane.

  5. Preparation and Application of Cationic Modified Cellulose Fibrils as a Papermaking Additive

    Directory of Open Access Journals (Sweden)

    Yanhong Gao


    Full Text Available This paper deals with cationic modified cellulose fibrils obtained by reacting the cellulose fibrils with 2,3-epoxypropyltrimethylammonium chloride (EPTMAC. The physical and chemical properties of unmodified cellulose fibrils (UMCF and cationic modified cellulose fibrils (CMCF were characterized by SEM, FTIR, degree of substitution, colloid titration, zeta potential, and thermogravimetric analysis. The experimental results showed that, after cationization, surface charge density and zeta potential reversed, thermal stability decreased, and new functional groups appeared, while the surface morphology did not show much difference from the UMCF. With the addition of three kinds of additives (UMCF, CMCF, and cationic starch (CS to BCTMP, the addition of UMCF and CMCF had little effect on zeta potential, while the addition of CS changed zeta potential obviously. With the increasing of additive amount, the bulk of paper sheets added CMCF did not change obviously, while the bulk of paper sheets added UMCF and CS decreased rapidly. With regard to physical strength, all the three kinds of additives could improve the tensile index and tear index; the tensile index of paper sheets added CS was higher than that of added UMCF and CMCF, while the tear index of paper sheets added CMCF was the highest among the three additives.

  6. On the Nature of the Intermediates and the Role of Chloride Ions in Pd-Catalyzed Allylic Alkylations: Added Insight from Density Functional Theory

    DEFF Research Database (Denmark)

    Fristrup, Peter; Ahlquist, Mårten Sten Gösta; Tanner, David Ackland


    The reactivity of intermediates in palladium-catalyzed allylic alkylation was investigated using DFT (B3LYP) calculations including a PB-SCRF solvation model. In the presence of both phosphine and chloride ligands, the allyl intermediate is in equilibrium between a cationic eta(3)-allylPd complex...... with two phosphine ligands, the corresponding neutral complex with one phosphine and one chloride ligand, and a neutral eta(1)-allylPd complex with one chloride and two phosphine ligands. The eta(1)-complex is unreactive toward nucleophiles. The cationic eta(3)-complex is the intermediate most frequently...... invoked in the title reaction, but in the presence of halides, the neutral, unsymmetrically substituted eta(3)-CoMplex will be formed rapidly from anionic Pd(0) complexes in solution. Since the latter will prefer both leaving group ionization and reaction with nucleophiles in the position trans...

  7. Nanoscale cation motion in TaOx, HfOx and TiOx memristive systems (United States)

    Wedig, Anja; Luebben, Michael; Cho, Deok-Yong; Moors, Marco; Skaja, Katharina; Rana, Vikas; Hasegawa, Tsuyoshi; Adepalli, Kiran K.; Yildiz, Bilge; Waser, Rainer; Valov, Ilia


    A detailed understanding of the resistive switching mechanisms that operate in redox-based resistive random-access memories (ReRAM) is key to controlling these memristive devices and formulating appropriate design rules. Based on distinct fundamental switching mechanisms, two types of ReRAM have emerged: electrochemical metallization memories, in which the mobile species is thought to be metal cations, and valence change memories, in which the mobile species is thought to be oxygen anions (or positively charged oxygen vacancies). Here we show, using scanning tunnelling microscopy and supported by potentiodynamic current-voltage measurements, that in three typical valence change memory materials (TaOx, HfOx and TiOx) the host metal cations are mobile in films of 2 nm thickness. The cations can form metallic filaments and participate in the resistive switching process, illustrating that there is a bridge between the electrochemical metallization mechanism and the valence change mechanism. Reset/Set operations are, we suggest, driven by oxidation (passivation) and reduction reactions. For the Ta/Ta2O5 system, a rutile-type TaO2 film is believed to mediate switching, and we show that devices can be switched from a valence change mode to an electrochemical metallization mode by introducing an intermediate layer of amorphous carbon.

  8. Temperature-induced collapse of alkaline Earth cation-polyacrylate anion complexes. (United States)

    Lages, Sebastian; Schweins, Ralf; Huber, Klaus


    Polyacrylate anions are used to inhibit CaCO3 precipitation and may be a promising additive to control formation of inorganic nanoparticles. The origin of this applicability lies in specific interactions between the alkaline earth cations and the carboxylate functions along the polyacrylate chains. In the absence of CO32- anions, these interactions eventually cause precipitation of polyelectrolytes. Extended investigation of dilute sodium polyacrylate solutions approaching this precipitation threshold revealed a dramatic shrinking of the PA coil dimensions once the threshold is reached (Eur. Phys. J. E 2001, 5, 117). Recent isothermal calorimetric titration experiments by Antonietti et al. (Macromolecules 2004, 37, 3444) indicated that the driving force of this precipitation is entropic in nature. In the present work, we investigated the impact of temperature on the structural changes of dissolved polyacrylate chains decorated with alkaline earth cations. To this end, large polyacrylate chains were brought close to the precipitation threshold by the addition of distinct amounts of Ca2+ or Sr2+ cations. The resulting structural intermediates were then subjected to temperature variations in the range of 15 degrees C polyacrylate coils were recorded by means of light and neutron scattering. As a major result, we could unambiguously demonstrate that the coils can reversibly be collapsed and extended by increasing and decreasing the temperature, respectively.

  9. [Antioxidant activity of cationic whey protein isolate]. (United States)

    titova, M E; Komolov, S A; Tikhomirova, N A


    The process of lipid peroxidation (LPO) in biological membranes of cells is carried out by free radical mechanism, a feature of which is the interaction of radicals with other molecules. In this work we investigated the antioxidant activity of cationic whey protein isolate, obtained by the cation-exchange chromatography on KM-cellulose from raw cow's milk, in vitro and in vivo. In biological liquids, which are milk, blood serum, fetal fluids, contains a complex of biologically active substances with a unique multifunctional properties, and which are carrying out a protective, antimicrobial, regenerating, antioxidant, immunomodulatory, regulatory and others functions. Contents of the isolate were determined electrophoretically and by its biological activity. Cationic whey protein isolate included lactoperoxidase, lactoferrin, pancreatic RNase, lysozyme and angeogenin. The given isolate significantly has an antioxidant effect in model experimental systems in vitro and therefore may be considered as a factor that can adjust the intensity of lipid oxidation. In model solutions products of lipid oxidation were obtained by oxidation of phosphatidylcholine by hydrogen peroxide in the presence of a source of iron. The composition of the reaction mixture: 0,4 mM H2O2; 50 mcM of hemin; 2 mg/ml L-alpha-phosphatidylcholine from soybean (Sigma, German). Lipid peroxidation products were formed during the incubation of the reaction mixture for two hours at 37 degrees C. In our studies rats in the adaptation period immediately after isolation from the nest obtained from food given orally native cationic whey protein isolate at the concentration three times higher than in fresh cow's milk. On the manifestation of the antioxidant activity of cationic whey protein isolate in vivo evidence decrease of lipid peroxidation products concentration in the blood of rats from the experimental group receipt whey protein isolate in dos 0,6 mg/g for more than 20% (pwhey protein isolate has an

  10. Alkali cation specific adsorption onto fcc(111) transition metal electrodes. (United States)

    Mills, J N; McCrum, I T; Janik, M J


    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  11. On the role of salt type and concentration on the stability behavior of a monoclonal antibody solution. (United States)

    Arosio, Paolo; Jaquet, Baptiste; Wu, Hua; Morbidelli, Massimo


    Protein-salt interactions regulate protein solubility and stability and in particular several protein related processes, such as salting-out and aggregation. Using an IgG2 monoclonal antibody as a model multi-domain therapeutic protein, we have investigated the salt effect on the reversible formation of protein clusters with small aggregation number. The oligomer formation has been quantified by size exclusion chromatography (SEC). It is found that the salt effect is strongly ion specific and pH dependent. In particular, at pH 3.0 only anions affect the aggregation propensity, while at pH 4.0 both anions and cations influence the aggregation rate. The ranking of the anion effect follows the Hofmeister series with the only exception of sulfate, while that of the cation effect does not. In addition, a maximum of the aggregation propensity as a function of salt concentration is observed (i.e., presence of re-stabilization). By correlating the aggregation kinetics to the experimental investigation of protein structure and surface energy, it is shown that changes in pH and salt concentration induce aggregation not only through charge screening and various solvation forces, but also through the formation of protein intermediates characterized by partially ordered structures and certain degrees of hydrophobicity. The complex interaction between the solvation forces and such protein secondary structures induced by salts explains the observed experimental results relative to re-stabilization at large salt concentrations, ion specificity and the peculiar behavior of the sulfate anion.

  12. Identification of a Chemoreceptor for Tricarboxylic Acid Cycle Intermediates (United States)

    Lacal, Jesús; Alfonso, Carlos; Liu, Xianxian; Parales, Rebecca E.; Morel, Bertrand; Conejero-Lara, Francisco; Rivas, Germán; Duque, Estrella; Ramos, Juan L.; Krell, Tino


    We report the identification of McpS as the specific chemoreceptor for 6 tricarboxylic acid (TCA) cycle intermediates and butyrate in Pseudomonas putida. The analysis of the bacterial mutant deficient in mcpS and complementation assays demonstrate that McpS is the only chemoreceptor of TCA cycle intermediates in the strain under study. TCA cycle intermediates are abundantly present in root exudates, and taxis toward these compounds is proposed to facilitate the access to carbon sources. McpS has an unusually large ligand-binding domain (LBD) that is un-annotated in InterPro and is predicted to contain 6 helices. The ligand profile of McpS was determined by isothermal titration calorimetry of purified recombinant LBD (McpS-LBD). McpS recognizes TCA cycle intermediates but does not bind very close structural homologues and derivatives like maleate, aspartate, or tricarballylate. This implies that functional similarity of ligands, such as being part of the same pathway, and not structural similarity is the primary element, which has driven the evolution of receptor specificity. The magnitude of chemotactic responses toward these 7 chemoattractants, as determined by qualitative and quantitative chemotaxis assays, differed largely. Ligands that cause a strong chemotactic response (malate, succinate, and fumarate) were found by differential scanning calorimetry to increase significantly the midpoint of protein unfolding (Tm) and unfolding enthalpy (ΔH) of McpS-LBD. Equilibrium sedimentation studies show that malate, the chemoattractant that causes the strongest chemotactic response, stabilizes the dimeric state of McpS-LBD. In this respect clear parallels exist to the Tar receptor and other eukaryotic receptors, which are discussed. PMID:20498372

  13. Interaction between cationic and conventional nonionic surfactants in the mixed micelle and monolayer formed in aqueous medium

    Directory of Open Access Journals (Sweden)

    Nabel A. Negm


    Full Text Available Mixed micellization and surface properties of cationic and nonionic surfactants dimethyl decyl-, tetradecyl- and hexadecyl phosphineoxide mixtures are studied using conductivity and surface tension measurements. The models of Rubingh, Rosen, and Clint, are used to obtain the interaction parameter, minimum area per molecule, mixed micelle composition, free energies of mixing and activity coefficients. The micellar mole fractions were always higher than ideal values indicating high contributions of cationics in mixed micelles. Activity coefficients were less than unity indicating synergism in micelles. The negative free energies of mixing showed the stability of the surfactants in the mixed micelles.

  14. Tuning light emission of PbS nanocrystals from infrared to visible range by cation exchange

    KAUST Repository

    Binetti, Enrico


    Colloidal semiconductor nanocrystals, with intense and sharp-line emission between red and near-infrared spectral regions, are of great interest for optoelectronic and bio-imaging applications. The growth of an inorganic passivation layer on nanocrystal surfaces is a common strategy to improve their chemical and optical stability and their photoluminescence quantum yield. In particular, cation exchange is a suitable approach for shell growth at the expense of the nanocrystal core size. Here, the cation exchange process is used to promote the formation of a CdS passivation layer on the surface of very small PbS nanocrystals (2.3 nm in diameter), blue shifting their optical spectra and yielding luminescent and stable nanostructures emitting in the range of 700–850 nm. Structural, morphological and compositional investigation confirms the nanocrystal size contraction after the cation-exchange process, while the PbS rock-salt crystalline phase is retained. Absorption and photoluminescence spectroscopy demonstrate the growth of a passivation layer with a decrease of the PbS core size, as inferred by the blue-shift of the excitonic peaks. The surface passivation strongly increases the photoluminescence intensity and the excited state lifetime. In addition, the nanocrystals reveal increased stability against oxidation over time. Thanks to their absorption and emission spectral range and the slow recombination dynamics, such highly luminescent nano-objects can find interesting applications in sensitized photovoltaic cells and light-emitting devices.

  15. Chabazite: stable cation-exchanger in hyper alkaline concrete pore water. (United States)

    Van Tendeloo, Leen; Wangermez, Wauter; Kurttepeli, Mert; de Blochouse, Benny; Bals, Sara; Van Tendeloo, Gustaaf; Martens, Johan A; Maes, André; Kirschhock, Christine E A; Breynaert, Eric


    To avoid impact on the environment, facilities for permanent disposal of hazardous waste adopt multibarrier design schemes. As the primary barrier very often consists of cement-based materials, two distinct aspects are essential for the selection of suitable complementary barriers: (1) selective sorption of the contaminants in the repository and (2) long-term chemical stability in hyperalkaline concrete-derived media. A multidisciplinary approach combining experimental strategies from environmental chemistry and materials science is therefore essential to provide a reliable assessment of potential candidate materials. Chabazite is typically synthesized in 1 M KOH solutions but also crystallizes in simulated young cement pore water, a pH 13 aqueous solution mainly containing K(+) and Na(+) cations. Its formation and stability in this medium was evaluated as a function of temperature (60 and 85 °C) over a timeframe of more than 2 years and was also asessed from a mechanistic point of view. Chabazite demonstrates excellent cation-exchange properties in simulated young cement pore water. Comparison of its Cs(+) cation exchange properties at pH 8 and pH 13 unexpectedly demonstrated an increase of the KD with increasing pH. The combined results identify chabazite as a valid candidate for inclusion in engineered barriers for concrete-based waste disposal.

  16. Dehydration and Stabilization of a Reactive Tertiary Hydroxyl Group in Solid Oral Dosage Forms of BMS-779788. (United States)

    Adams, Monica L; Sharma, Vijayata; Gokhale, Madhushree; Huang, Yande; Stefanski, Kevin; Su, Ching; Hussain, Munir A


    BMS-779788 contains a reactive tertiary hydroxyl attached to a weakly basic imidazole ring. Propensity of the carbinol toward dehydration to yield the corresponding alkene, BMS-779788-ALK, was evaluated. Elevated levels of BMS-779788-ALK were observed in excipient compatibility samples. Stability studies revealed that BMS-779788 degrades to BMS-779788-ALK in capsules and tablets prepared by both dry and wet granulation processes. An acid-catalyzed dehydration mechanism, in which the heterocyclic core contributes resonance stability to the cationic intermediate via charge transfer to the imidazole ring, was proposed. Therefore, neutralization via a buffered (pH 7.0) granulating solution was used to mitigate dehydration. Solution studies revealed degradation of BMS-779788 to BMS-779788-ALK over the pH range of 1-7.5. Reversibility was confirmed by initiating reactions with BMS-779788-ALK over the same pH range. Accordingly, a simple reversible scheme can be used to describe reactions initiated with either BMS-779788 or BMS-779788-ALK. To eliminate potential for charge delocalization across the heterocycle and probe the degradation mechanism, the imidazole ring of BMS-779788 was methylated (BMS-779788-Me). The propensity for acid-catalyzed dehydration was then evaluated. The acid stability of BMS-779788-Me confirmed that the heterocyclic core contributes to reactivity liability of the tertiary hydroxyl.

  17. Biocatalysis: synthesis of chiral intermediates for drugs. (United States)

    Patel, Ramesh N


    Chirality is a key factor in the safety and efficacy of many drug products and thus the production of single enantiomers of drug intermediates has become increasingly important in the pharmaceutical industry. Chiral intermediates and fine chemicals are in high demand for the bulk preparation of drug substances and agricultural products. There has been an increasing awareness of the enormous potential of the use of microorganisms and microorganism-derived enzymes for the transformation of synthetic chemicals with high chemo-, regio- and enantioselectivities. In this article, biocatalytic processes are described for the synthesis of chiral intermediates for drugs.

  18. Language in use intermediate : classroom book

    CERN Document Server

    Doff, Adrian


    ach of the four levels comprises about 80 hours of class work, with additional time for the self-study work. The Teacher's Book contains all the pages from the Classroom Book, with interleaved teaching notes including optional activities to cater for different abilities. There is a video to accompany the Beginner, Pre-intermediate and Intermediate levels. Each video contains eight stimulating and entertaining short programmes, as well as a booklet of photocopiable activities. Free test material is available in booklet and web format for Beginner and Pre-intermediate levels. Visit or contact your local Cambridge University Press representative.

  19. Language in use intermediate : teacher's book

    CERN Document Server

    Doff, Adrian


    Each of the four levels comprises about 80 hours of class work, with additional time for the self-study work. The Teacher's Book contains all the pages from the Classroom Book, with interleaved teaching notes including optional activities to cater for different abilities. There is a video to accompany the Beginner, Pre-intermediate and Intermediate levels. Each video contains eight stimulating and entertaining short programmes, as well as a booklet of photocopiable activities. Free test material is available in booklet and web format for Beginner and Pre-intermediate levels. Visit or contact your local Cambridge University Press representative.

  20. Interaction between alginates and manganese cations: identification of preferred cation binding sites. (United States)

    Emmerichs, N; Wingender, J; Flemming, H-C; Mayer, C


    Algal and bacterial alginates have been studied by means of 13C NMR spectroscopy in presence of paramagnetic manganese ions in order to reveal the nature of their interaction with bivalent cations. It is found that the mannuronate blocks bind manganese cations externally near their carboxylate groups, while guluronate blocks show the capability to integrate Mn2+ into pocket-like structures formed by adjacent guluronate residues. In alternating mannuronate-guluronate blocks, manganese ions preferentially locate in a concave structure formed by guluronate-mannuronate pairs. Partial acetylation of the alginate generally reduces its capability to interact with bivalent cations, however, the selectivity of the binding geometry is conserved. The results may serve as a hint for the better understanding of the alginate gelation in presence of calcium ions.

  1. Electronic and vibrational spectroscopy of intermediates in methane-to-methanol conversion by CoO+ (United States)

    Altinay, Gokhan; Kocak, Abdulkadir; Silva Daluz, Jennifer; Metz, Ricardo B.


    At room temperature, cobalt oxide cations directly convert methane to methanol with high selectivity but very low efficiency. Two potential intermediates of this reaction, the [HO-Co-CH3]+ insertion intermediate and [H2O-Co=CH2]+ aquo-carbene complex are produced in a laser ablation source and characterized by electronic and vibrational spectroscopy. Reaction of laser-ablated cobalt cations with different organic precursors seeded in a carrier gas produces the intermediates, which subsequently expand into vacuum and cool. Ions are extracted into a time-of-flight mass spectrometer and spectra are measured via photofragment spectroscopy. Photodissociation of [HO-Co-CH3]+ in the visible and via infrared multiple photon dissociation (IRMPD) makes only Co+ + CH3OH, while photodissociation of [H2O-Co=CH2]+ produces CoCH2+ + H2O. The electronic spectrum of [HO-Co-CH3]+ shows progressions in the excited state Co-C stretch (335 cm-1) and O-Co-C bend (90 cm-1); the IRMPD spectrum gives νOH = 3630 cm-1. The [HO-Co-CH3]+(Ar) complex has been synthesized and its vibrational spectrum measured in the O-H stretching region. The resulting spectrum is sharper than that obtained via IRMPD and gives νOH = 3642 cm-1. Also, an improved potential energy surface for the reaction of CoO+ with methane has been developed using single point energies calculated by the CBS-QB3 method for reactants, intermediates, transition states and products.

  2. Aquatic toxicity and biodegradability of advanced cationic surfactant APA-22 compatible with the aquatic environment. (United States)

    Yamane, Masayuki; Toyo, Takamasa; Inoue, Katsuhisa; Sakai, Takaya; Kaneko, Youhei; Nishiyama, Naohiro


    Cationic surfactant is a chemical substance used in hair conditioner, fabric softener and other household products. By investigating the relationship between the aquatic toxicity and the chemical structures of two types of mono alkyl cationic surfactants, alkyl trimethylammonium salts and alkyl dimethylamine salts, we have found that the C22 alkyl chain length is effective to reduce the toxicity. Besides, we have recognized that the amidopropyl functional group contributes to the enhanced biodegradability by investigating the biodegradation trend of (alkylamidopropyl)dimethylamine salt (alkyl chain length: C18). Based on these findings, we have developed mono alkyl cationic surfactant called APA-22, N-[3-(dimethylamino)propyl]docosanamide salt. APA-22 is formed by the C22 alkyl chain, amidopropyl functional group and di-methyltertiary amine group. We evaluated the aerobic and anaerobic biodegradability of APA-22 by two standard methods (OECD Test Guideline 301B and ECETOC technical document No.28) and found that this substance was degraded rapidly in both conditions. The toxicity to algae, invertebrate and fish of this substance are evaluated by using OECD Test Guideline 201, 202 and 203, respectively. All acute toxicity values are >1 mg/L, which indicates that environmental toxicity of this substance is relatively less toxic to aquatic organism. In addition, we estimated the biodegradation pathway of APA-22 and observed the complete disappearance of APA-22 and its intermediates during the test periods. Based on the environmental data provided above, we concluded that APA22 is more compatible with the aquatic environment compared to other cationic surfactants with mono long alkyl chain.

  3. Soil Stabilization Using Lime: Advantages, Disadvantages and Proposing a Potential Alternative


    Ibtehaj Taha Jawad; Mohd Raihan Taha; Zaid Hameed Majeed; Tanveer A Khan


    This study is an overview of previous studies on lime (quick and hydrated) -treated soil. Lime is the oldest traditional stabilizer used for soil stabilization. The mechanism of soil-lime treatment involves cation exchange, which leads to the flocculation and agglomeration of soil particles. The high pH environment then causes a pozzolanic reaction between the free Ca+2 cations and the dissolved silica and alumina. Lime-treated soil effectively increases the strength, durability and workabili...

  4. Epitope mapping of imidazolium cations in ionic liquid-protein interactions unveils the balance between hydrophobicity and electrostatics towards protein destabilisation. (United States)

    Silva, Micael; Figueiredo, Angelo Miguel; Cabrita, Eurico J


    We investigated imidazolium-based ionic liquid (IL) interactions with human serum albumin (HSA) to discern the level of cation interactions towards protein stability. STD-NMR spectroscopy was used to observe the imidazolium IL protons involved in direct binding and to identify the interactions responsible for changes in Tm as accessed by differential scanning calorimetry (DSC). Cations influence protein stability less than anions but still significantly. It was found that longer alkyl side chains of imidazolium-based ILs (more hydrophobic) are associated with a higher destabilisation effect on HSA than short-alkyl groups (less hydrophobic). The reason for such destabilisation lies on the increased surface contact area of the cation with the protein, particularly on the hydrophobic contacts promoted by the terminus of the alkyl chain. The relevance of the hydrophobic contacts is clearly demonstrated by the introduction of a polar moiety in the alkyl chain: a methoxy or alcohol group. Such structural modification reduces the degree of hydrophobic contacts with HSA explaining the lesser extent of protein destabilisation when compared to longer alkyl side chain groups: above [C2mim](+). Competition STD-NMR experiments using [C2mim](+), [C4mim](+) and [C2OHmim](+) also validate the importance of the hydrophobic interactions. The combined effect of cation and anion interactions was explored using (35)Cl NMR. Such experiments show that the nature of the cation has no influence on the anion-protein contacts, still the nature of the anion modulates the cation-protein interaction. Herein we propose that more destabilising anions are likely to be a result of a partial contribution from the cation as a direct consequence of the different levels of interaction (cation-anion pair and cation-protein).

  5. Physical Mechanisms for Earthquakes at Intermediate Depths (United States)

    Green, H. W.; Green, H. W.


    Conventional brittle shear failure it is strongly inhibited by pressure because it relies on local tensile failure. In contrast, plastic flow processes are thermally activated, making them sensitive functions of temperature, but their pressure dependence is only moderate. As a consequence, in Earth, faulting by unassisted brittle failure is probably restricted to depths less than ~ 30 km because the rocks flow at lower stresses than they fracture. To enable faulting at greater depths, mineral reactions must occur that generate a fluid or fluid-like solid that is much weaker than the parent assemblage. Although a variety of plastic instabilities have been and continue to be proposed to explain earthquakes at depth, dehydration embrittlement remains the only experimentally verified faulting mechanism consistent with the pressures and compositions existing at depths of 50-300km within subducting lithosphere. However, low pressure hydrous phases potentially abundant in subducting lithosphere (e.g. chlorite and antigorite) exhibit a temperature maximum in their stability, implying that the bulk volume change at depths of more than 70-100 km. becomes negative, thereby raising questions about mechanical instability upon dehydration. Further, it is now well-accepted that intermediate-depth earthquakes occur within the descending slab (double seismic zones present in several slabs dramatically demonstrate this fact), in conflict with the maximum depth of 10-12 km accepted for hydration of the lithosphere at oceanic spreading centers. Thus, on the one hand these earthquakes may be evidence that hydrous phases exist deep within subducting slabs but on the other hand, a mechanism for hydration to such depths is not known. One possibility is that large earthquakes outboard of trenches break the surface and allow hydration of the fault zone that can later dehydrate to yield earthquakes at depth, but no mechanism is known for pumping H2O into such fault zones to depths of tens of

  6. The second national audit of intermediate care. (United States)

    Young, John; Gladman, John R F; Forsyth, Duncan R; Holditch, Claire


    Intermediate care services have developed internationally to expedite discharge from hospital and to provide an alternative to an emergency hospital admission. Inconsistencies in the evidence base and under-developed governance structures led to concerns about the care quality, outcomes and provision of intermediate care in the NHS. The National Audit of Intermediate Care was therefore established by an interdisciplinary group. The second national audit reported in 2013 and included crisis response teams, home-based and bed-based services in approximately a half of the NHS. The main findings were evidence of weak local strategic planning, considerable under-provision, delays in accessing the services and lack of mental health involvement in care. There was a very high level of positive patient experience reported across all types of intermediate care, though reported involvement with care decisions was less satisfactory.

  7. Intermediate/Advanced Research Design and Statistics (United States)

    Ploutz-Snyder, Robert


    The purpose of this module is To provide Institutional Researchers (IRs) with an understanding of the principles of advanced research design and the intermediate/advanced statistical procedures consistent with such designs

  8. Directional spread parameter at intermediate water depth

    Digital Repository Service at National Institute of Oceanography (India)

    SanilKumar, V.; Deo, M.C.; Anand, N.M.; AshokKumar, K.

    The characteristics of directional spread parameters at intermediate water depth are investigated based on a cosine power '2s' directional spreading model. This is based on wave measurements carried out using a Datawell directional waverider buoy...

  9. Conformational energetics of cationic backbone rearrangements in triterpenoid biosynthesis provide an insight into enzymatic control of product. (United States)

    Kürti, László; Chein, Rong-Jie; Corey, E J


    2,3-( S)-Oxidosqualene (C 30H 50O) serves as a versatile starting point for the remarkable biosynthesis of many isomeric naturally occurring triterpenoids of formula C 30H 50O. These biosyntheses all involve polycyclization via cationic intermediates. The fully cyclized primary products then are converted to various structures by cationic rearrangements involving the polycyclic backbone. The energetics of these rearrangements has been examined by B3LYP 6-31 G* DFT calculations and by ab initio Hartree-Fock calculations at the 6-31G* or 3-21G(*) level. The results have led to the conclusion that the biosynthesis of friedelin, the most drastically rearranged of the pentacyclic triterpenes, involves a complex nonstop process, with no stable intermediates between 2,3-( S)-oxidosqualene and friedelin. It is proposed that this single-reaction biosynthesis consists of pentacyclization to the lupanyl cation followed directly by a sequence of 10 suprafacial 1,2-shifts of carbon and hydrogen, driven by the large exergonicity of the pentacyclization and electrostatic acceleration of the rearrangement steps.

  10. Ionic liquids based on S-alkylthiolanium cations and TFSI anion as potential electrolytes

    Institute of Scientific and Technical Information of China (English)

    ZHANG HuanQi; YANG Li; FANG ShaoHua; PENG ChengXin; LUO HongJun


    New ionic liquids based on S-alkylthiolanium cations with TFSI anions were synthesized and charac-terized.The physical and electrochemical properties,including melting point,thermal stability,solubil-ity,viscosity,conductivity and electrochemical window,were reported.Relation between these proper-ties and the structure of the cations was discussed.In this series,T4TFSI and T5TFSI have melting points below -60℃,and their conductivities are 2.10 mS/cm and 1.46 mS/cm;their electrochemical windows are 4.1 V and 4.5 V at room temperature.These cyclic alkylthiolanium-based ionic liquids are promising as novel electrolytes in various electrochemical devices,especially under low temperature condition.

  11. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.


    Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or

  12. Heart imaging with cationic complexes of technetium

    Energy Technology Data Exchange (ETDEWEB)

    Deutsch, E.; Bushong, W.; Glavan, K.A.; Elder, R.C.; Sodd, V.J.; Scholz, K.L.; Fortman, D.L.; Lukes, S.J.


    The cationic technetium-99 complex trans-(99TC(dmpe)2Cl2)+, where dmpe is bis(1,2-dimethylphosphino)ethane or (CH3)2P-CH2-P(CH3)2, has been prepared and characterized by single-crystal, x-ray structural analysis. The technetium-99m analog, trans-(99mTc(dmpe) 2Cl2)+, has also been prepared and shown to yield excellent gamma-ray images of the heart. The purposeful design, characterization, and synthesis of this technetium-99m radiopharmaceutical represents a striking application of fundamental inorganic chemistry to a problem in applied nuclear medicine.

  13. Formation of cobalt hydrotalcite by cation exchange of Co2+-substitued zeolite X (United States)

    Jeong, H. Y.; Lee, K.


    Zeolite has been utilized to sequester heavy metals and nuclides due to the high cation exchange capacity. However, once-immobilized cations by zeolite tend to be re-exchanged by other cations (Ca2+, Mg2+, Na+, etc) present in groundwater. Thus, it is important to understand the mechanism associated with re-exchange reactions to predict the environmental fate and behavior of the metal cations sequestered by zeolite. In this study, we performed a series of cation exchange experiments using Co2+-substituted zeolite X (Co-X) in concentrated CaCl2 solutions. The radioactive isotope of cobalt (60Co2+), commonly found in low-to-intermediate level nuclear wastes, undergoes radioactive decay, likely altering the physicochemical properties of zeolite by generating heat and irradiation. To simulate such effects, Co-X was thermally treated at 400 and 600oC before re-exchange experiments. At the higher treatment temperature, the re-exchanged amount of Co2+ in Co-X by Ca2+ was found to decrease. According to X-ray diffraction, the re-exchange led to little change in the zeolite crystallinity for thermally untreated samples, but the significantly decreased crystallinity was noted for re-exchanged, thermally treated samples. Nonetheless, 27Al MAS NMR spectra of all re-exchanged samples revealed that the peaks corresponding to 4-fold coordinated Al became broader with their position shifting as a result of the re-exchange, suggesting that the re-exchange caused a short-range order structural distortion for both thermally untreated and treated samples. Also, Co-K edge X-ray absorption spectroscopy (XAS) was employed to examine the mechanism(s) involved in the re-exchange. By comparison of XAS spectra between re-exchanged samples and model compounds, Co2+ was likely to be either present as an extraframwork cation within zeolite or incorporated into a cobalt hydrotalcite (Co6Al2(OH)16(An-)2/n where An- is an interlayer anion) phase. The relative contribution of an extraframwork Co2

  14. Influence of the Ion Coordination Number on Cation Exchange Reactions with Copper Telluride Nanocrystals. (United States)

    Tu, Renyong; Xie, Yi; Bertoni, Giovanni; Lak, Aidin; Gaspari, Roberto; Rapallo, Arnaldo; Cavalli, Andrea; Trizio, Luca De; Manna, Liberato


    Cu2-xTe nanocubes were used as starting seeds to access metal telluride nanocrystals by cation exchanges at room temperature. The coordination number of the entering cations was found to play an important role in dictating the reaction pathways. The exchanges with tetrahedrally coordinated cations (i.e., with coordination number 4), such as Cd(2+) or Hg(2+), yielded monocrystalline CdTe or HgTe nanocrystals with Cu2-xTe/CdTe or Cu2-xTe/HgTe Janus-like heterostructures as intermediates. The formation of Janus-like architectures was attributed to the high diffusion rate of the relatively small tetrahedrally coordinated cations, which could rapidly diffuse in the Cu2-xTe NCs and nucleate the CdTe (or HgTe) phase in a preferred region of the host structure. Also, with both Cd(2+) and Hg(2+) ions the exchange led to wurtzite CdTe and HgTe phases rather than the more stable zinc-blende ones, indicating that the anion framework of the starting Cu2-xTe particles could be more easily deformed to match the anion framework of the metastable wurtzite structures. As hexagonal HgTe had never been reported to date, this represents another case of metastable new phases that can only be accessed by cation exchange. On the other hand, the exchanges involving octahedrally coordinated ions (i.e., with coordination number 6), such as Pb(2+) or Sn(2+), yielded rock-salt polycrystalline PbTe or SnTe nanocrystals with Cu2-xTe@PbTe or Cu2-xTe@SnTe core@shell architectures at the early stages of the exchange process. In this case, the octahedrally coordinated ions are probably too large to diffuse easily through the Cu2-xTe structure: their limited diffusion rate restricts their initial reaction to the surface of the nanocrystals, where cation exchange is initiated unselectively, leading to core@shell architectures. Interestingly, these heterostructures were found to be metastable as they evolved to stable Janus-like architectures if annealed at 200 °C under vacuum.

  15. Stability Functions

    CERN Document Server

    Burns, Daniel; Wang, Zuoqin


    In this article we discuss the role of stability functions in geometric invariant theory and apply stability function techniques to problems in toric geometry. In particular we show how one can use these techniques to recover results of Burns-Guillemin-Uribe and Shiffman-Tate-Zelditch on asymptotic properties of sections of holomorphic line bundles over toric varieties.

  16. Targeting the S1 and S3 subsite of trypsin with unnatural cationic amino acids generates antimicrobial peptides with potential for oral administration. (United States)

    Karstad, Rasmus; Isaksen, Geir; Wynendaele, Evelien; Guttormsen, Yngve; De Spiegeleer, Bart; Brandsdal, Bjørn-Olav; Svendsen, John Sigurd; Svenson, Johan


    This study investigates how the S1 and S3 site of trypsin can be challenged with cationic amino acid analogues to yield active antimicrobial peptides with stability toward tryptic degradation. It is shown that unnatural analogues can be incorporated to generate stable peptides with maintained bioactivity to allow for a potential oral uptake. Selected peptides were studied using isothermal calorimetry and computational methods. Both stable and unstable peptides were found to bind stoichiometrically to trypsin with dissociation constants ranging 2-60 μM, suggesting several different binding modes. The stability of selected peptides was analyzed in whole organ extracts and the incorporation of homoarginine and 2-amino-(3-guanidino)propanoic acid resulted in a 14- and 50-fold increase in duodenal stability. In addition, a 40- and 70-fold increase in stomach stability is also reported. Overall, these results illustrate how the incorporation of cationic side chains can be employed to generate bioactive peptides with significant systemic stability.

  17. Ionothermal synthesis and electrochemical properties of a selenidostannate containing the mixed cations of Na+ and enH+ (United States)

    Du, Cheng-Feng; Li, Jian-Rong; Shen, Nan-Nan; Huang, Xiao-Ying


    In this report, by taking advantages of the competitive and synergistic effects of mixed-cations under the ionothermal conditions, a novel selenidostannate compound containing the mixed cations, namely (enH)3Na[Sn3Se7]2·1.5Me2NH·1.5H2O (1, en=ethylenediamine, Me2NH=dimethylamine) was obtained in the presence of the ionic liquid (IL) [DAMS]I (4-N,N-Dimethylamino-4‧-N‧-methylstilbazolium iodide) with a bulky and more structurally rigid organic cation as the main solvent and en as the auxiliary solvent. The compound features anionic [Sn3Se7]n2n- layers that are interconnected by sodium ions to form a three-dimensional (3D) structure. The syntheses, structure, thermal, optical and electrochemical properties of 1 were investigated. 1 showed good thermal stability and a Na+ ion storage property without capacity fading over 150 cycles.


    Institute of Scientific and Technical Information of China (English)

    Dong Zou; Xiu-fen Li; Xiao-li Zhu; Xiang-zheng Kong


    Cationic latexes were prepared through emulsion copolymerization of styrene (St) and butyl acrylate (BA) with a cationic surfactant,cetyl trimethyl ammonium bromide (CTAB).Latex properties,including particle size,size distribution,ζ potential,surface tension and monomer conversion,were determined for latexes prepared with different CTAB amounts.Evolution of these properties during emulsion polymerization was followed in order to understand the mechanism of the particles formation.Results showed that both particle size and ζpotential were function of polymerization time and latex solids.Parallel emulsion polymerizations with cationic,anionic charged initiator and charge-free initiators were also carried out,the latex properties were determined at different polymerization time.All these results were attentively interpreted based on the mechanisms of emulsion polymerization,surfactant adsorption and latex particle stabilization.

  19. Influence of the substitution of {beta}-cyclodextrins by cationic groups on the complexation of organic anions

    Energy Technology Data Exchange (ETDEWEB)

    Hbaieb, S. [U.R. Physico-Chimie des Materiaux Solides, Faculte des Sciences de Tunis, Manar II, 2092 Tunis (Tunisia)], E-mail:; Kalfat, R. [U.R. Physico-Chimie des Materiaux Solides, Faculte des Sciences de Tunis, Manar II, 2092 Tunis (Tunisia); Chevalier, Y. [Laboratoire d' Automatique et de Genie des Procedes (LAGEP), UMR 5007 CNRS-Universite Claude Bernard Lyon 1, 69622 Villeurbanne (France)], E-mail:; Amdouni, N. [U.R. Physico-Chimie des Materiaux Solides, Faculte des Sciences de Tunis, Manar II, 2092 Tunis (Tunisia); Parrot-Lopez, H. [Institut de Chimie et Biochimie Moleculaires et Supramoleculaires (ICBMS), UMR 5246 CNRS-Universite Claude Bernard Lyon 1, 69622 Villeurbanne (France)], E-mail:


    The inclusion complexation of the organic anion, dansyl-acid, by cationic derivatives of {beta}-cyclodextrin has been investigated. A series of cationic {beta}-cyclodextrins with various positive charge has been synthesized by selective functionalization of the primary face of {beta}-cyclodextrin with amino groups. The complexes were of the 1:1 stoichiometry; the stability constants (K{sub 11}) have been evaluated from UV-Vis measurements by application of the Benesi-Hildebrand equation. The presence of amino groups increased the complexation ability. {beta}-cyclodextrin fully substituted at the primary face with amino groups showed the strongest inclusion binding ability towards the dansyl-acid guest. The enhanced complexation for anions was ascribed to the cationic amino groups. A simple thermodynamic model of the electrostatic contribution to the complexation is presented.

  20. Effect of substrates and intermediate compounds on foaming in manure digestion systems

    DEFF Research Database (Denmark)

    Boe, Kanokwan; Kougias, Panagiotis; Pacheco, F.;


    Manure contains several compounds that can potentially cause foaming during anaerobic digestion. Understanding the effect of substrates and intermediate compounds on foaming tendency and stability could facilitate strategies for foaming prevention and recovery of the process. In this study......, the effect of physicochemical properties of substrates and intermediate compounds on liquid properties such as surface tension, surfactant property, and hydrophobicity were investigated and compared with the effect on foaming tendency and foam stability. The results showed that there was no consistent...... correlation between foaming potential and hydrophobicity, oil displacement area (ODA) or surface tension of the tested solutions, and the best way to determine the foaming property of the solution was to directly measure foaming tendency and foam stability. Na-oleate and acetic acid showed the highest...

  1. Radical cations of aromatic selenium compounds: role of Se···X nonbonding interactions. (United States)

    Singh, Beena G; Thomas, Elizabeth; Sawant, Shilpa N; Takahashi, Kohei; Dedachi, Kenchi; Iwaoka, Michio; Priyadarsini, K Indira


    Selenium centered radical cations in aliphatic selenium compounds are stabilized by formation of two-center-three electron (2c-3e) hemi bonds either with nearby heteroatoms forming monomer radicals or with selenium atoms of the parent molecules forming dimer radicals. Such radicals in aromatic selenium compounds would generally be stabilized as monomers by the delocalization of the spin density along the aromatic ring. To test the assumption if aromatic selenides having Se···X nonbonding interactions can show different types of radical cations, we have performed pulse radiolysis studies of three structurally related aromatic selenium compounds and the results have been substantiated with cyclic voltammetry and quantum chemical calculations. The three aromatic selenium compounds have functional groups like -CH2N(CH3)2 (1), -CH2OH (2), and -CH3 (3) at ortho position to the -SeCH3 moiety. The energy of Se···X nonbonding interactions (E(nb)) for these compounds is in the order 1 (Se···N) > 2 (Se···O) > 3 (Se···H). Radical cations, 1(•+), 2(•+) and 3(•+) were produced by the one-electron oxidation of 1, 2 and 3 by radiolytically generated (•)OH and Br2(•-) radicals. Results on transient spectra, lifetime, and secondary reactions of 1(•+), 2(•+), and 3(•+) indicated that 1(•+) shows a significantly different absorption spectrum, longer lifetime, and less oxidizing power compared to those of 2(•+) or 3(•+). Quantum chemical calculations suggested that 1(•+) is stabilized by the formation of a 2c-3e bond between Se and N atoms, whereas 2(•+) and 3(•+) acquire stability through the delocalization of the spin density on the aromatic ring. These results provide evidence for the first time that stronger nonbonding interactions between Se···N in the ground state, facilitate the formation of stabilized radical cations, which can significantly influence the redox chemistry and the biological activity of aromatic selenium compounds.

  2. Antibacterial Activity of Geminized Amphiphilic Cationic Homopolymers. (United States)

    Wang, Hui; Shi, Xuefeng; Yu, Danfeng; Zhang, Jian; Yang, Guang; Cui, Yingxian; Sun, Keji; Wang, Jinben; Yan, Haike


    The current study is aimed at investigating the effect of cationic charge density and hydrophobicity on the antibacterial and hemolytic activities. Two kinds of cationic surfmers, containing single or double hydrophobic tails (octyl chains or benzyl groups), and the corresponding homopolymers were synthesized. The antimicrobial activity of these candidate antibacterials was studied by microbial growth inhibition assays against Escherichia coli, and hemolysis activity was carried out using human red blood cells. It was interestingly found that the homopolymers were much more effective in antibacterial property than their corresponding monomers. Furthermore, the geminized homopolymers had significantly higher antibacterial activity than that of their counterparts but with single amphiphilic side chains in each repeated unit. Geminized homopolymers, with high positive charge density and moderate hydrophobicity (such as benzyl groups), combine both advantages of efficient antibacterial property and prominently high selectivity. To further explain the antibacterial performance of the novel polymer series, the molecular interaction mechanism is proposed according to experimental data which shows that these specimens are likely to kill microbes by disrupting bacterial membranes, leading them unlikely to induce resistance.

  3. Electronic absorptions of the benzylium cation (United States)

    Dryza, Viktoras; Chalyavi, Nahid; Sanelli, Julian A.; Bieske, Evan J.


    The electronic transitions of the benzylium cation (Bz+) are investigated over the 250-550 nm range by monitoring the photodissociation of mass-selected C7H7+-Arn (n = 1, 2) complexes in a tandem mass spectrometer. The Bz+-Ar spectrum displays two distinct band systems, the S1←S0 band system extending from 370 to 530 nm with an origin at 19 067 ± 15 cm-1, and a much stronger S3←S0 band system extending from 270 to 320 nm with an origin at 32 035 ± 15 cm-1. Whereas the S1←S0 absorption exhibits well resolved vibrational progressions, the S3←S0 absorption is broad and relatively structureless. Vibronic structure of the S1←S0 system, which is interpreted with the aid of time-dependent density functional theory and Franck-Condon simulations, reflects the activity of four totally symmetric ring deformation modes (ν5, ν6, ν9, ν13). We find no evidence for the ultraviolet absorption of the tropylium cation, which according to the neon matrix spectrum should occur over the 260 - 275 nm range [A. Nagy, J. Fulara, I. Garkusha, and J. Maier, Angew. Chem., Int. Ed. 50, 3022 (2011)], 10.1002/anie.201008036.

  4. Cationic Antimicrobial Polymers and Their Assemblies

    Directory of Open Access Journals (Sweden)

    Ana Maria Carmona-Ribeiro


    Full Text Available Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs. The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

  5. The distonic ion (·)CH 2CH 2CH (+)OH, keto ion CH 3CH 2CH=O (+·), enol ion CH 3CH=CHOH (+·), and related C 3H 6O (+·) radical cations. Stabilities and isomerization proclivities studied by dissociation and neutralization-reionization. (United States)

    Polce, M J; Wesdemiotis, C


    Metastable ion decompositions, collision-activated dissociation (CAD), and neutralization-reionization mass spectrometry are utilized to study the unimolecular chemistry of distonic ion (·)CH2CH2CH(-)OH (2(+·)) and its enol-keto tautomers CH3CH=CHOH(-·) (1 (+·)) and CH3CH2CH=O (+·) (3(+·)). The major fragmentation of metastable 1(+·)-3(+·) is H(·) loss to yield the propanoyl cation, CH3CH2C≡O(+). This reaction remains dominant upon collisional activation, although now some isomeric CH2=CH-CH(+) OH is coproduced from all three precursors. The CAD and neutralization-reionization ((+)NR(+)) spectra of keto ion 3 (+·) are substantially different from those of tautomers 2(+·) and 1(+·). Hence, 3(+·) without sufficient energy for decomposition (i. e. , "stable" 3(+·)) does not isomerize to the ther-modynamically more stable ions 2(+·) or 1(+·), and the 1,4-H rearrangement H-CH2CH2CH=O(+·)(3 (+·)) → CH2CH2CH(+) O-H (2 (+·)) must require an appreciable critical energy. Although the fragment ion abundances in the (+) NR (+) (and CAD) spectra of 1 (+·) and 2 (+·) are similar, the relative and absolute intensities of the survivor ions (recovered C3H6O(+·) ions in the (+)NR(+) spectra) are markedly distinct and independent of the internal energy of 1 (+·) and 2 (+·). Furthermore, 1 (+·) and 2 (+·) show different MI spectra. Based on these data, distonic ion 2 (+·) does not spontaneously rearrange to enol ion 1 (+·) (which is the most stable C3H6O(+·) of CCCO connectivity) and, therefore, is separated from it by an appreciable barrier. In contrast, the molecular ions of cyclopropanol (4 (+·)) and allyl alcohol (5 (+·)) isomerize readily to 2 (+·), via ring opening and 1,2-H(-) shift, respectively. The sample found to generate the purest 2 (+·) is α-hydroxy-γ-butyrolactone. Several other precursors that would yield 2 (+·) by a least-motion reaction cogenerate detectable quantities of enol ion 1 (+·), or the enol ion of acetone (CH2=C(CH3

  6. Sulfation and Cation Effects on the Conformational Properties of the Glycan Backbone of Chondroitin Sulfate Disaccharides (United States)

    Faller, Christina E.; Guvench, Olgun


    Chondroitin sulfate (CS) is one of several glycosaminoglycans that are major components of proteoglycans. A linear polymer consisting of repeats of the disaccharide -4GlcAβ1-3GalNAcβ1-, CS undergoes differential sulfation resulting in five unique sulfation patterns. Because of the dimer repeat, the CS glycosidic “backbone” has two distinct sets of conformational degrees of freedom defined by pairs of dihedral angles: (ϕ1, ψ1) about the β1-3 glycosidic linkage and (ϕ2, ψ2) about the β1-4 glycosidic linkage. Differential sulfation and the possibility of cation binding, combined with the conformational flexibility and biological diversity of CS, complicate experimental efforts to understand CS three-dimensional structures at atomic resolution. Therefore, all-atom explicit-solvent molecular dynamics simulations with Adaptive Biasing Force sampling of the CS backbone were applied to obtain high resolution, high precision free energies of CS disaccharides as a function of all possible backbone geometries. All ten disaccharides (β1-3 vs. β1-4 linkage x five different sulfation patterns) were studied; additionally, ion effects were investigated by considering each disaccharide in the presence of either neutralizing sodium or calcium cations. GlcAβ1-3GalNAc disaccharides have a single, broad, thermodynamically important free-energy minimum whereas GalNAcβ1-4GlcA disaccharides have two such minima. Calcium cations but not sodium cations bind to the disaccharides, and binding is primarily to the GlcA –COO− moiety as opposed to sulfate groups. This binding alters the glycan backbone thermodynamics in instances where a calcium cation bound to –COO− can act to bridge and stabilize an interaction with an adjacent sulfate group, whereas, in the absence of this cation, the proximity of a sulfate group to –COO− results in two like charges being both desolvated and placed adjacent to each other and is found to be destabilizing. In addition to providing

  7. Dynamics of the bacterial intermediate filament crescentin in vitro and in vivo.

    Directory of Open Access Journals (Sweden)

    Osigwe Esue

    Full Text Available BACKGROUND: Crescentin, the recently discovered bacterial intermediate filament protein, organizes into an extended filamentous structure that spans the length of the bacterium Caulobacter crescentus and plays a critical role in defining its curvature. The mechanism by which crescentin mediates cell curvature and whether crescentin filamentous structures are dynamic and/or polar are not fully understood. METHODOLOGY/PRINCIPAL FINDINGS: Using light microscopy, electron microscopy and quantitative rheology, we investigated the mechanics and dynamics of crescentin structures. Live-cell microscopy reveals that crescentin forms structures in vivo that undergo slow remodeling. The exchange of subunits between these structures and a pool of unassembled subunits is slow during the life cycle of the cell however; in vitro assembly and gelation of C. crescentus crescentin structures are rapid. Moreover, crescentin forms filamentous structures that are elastic, solid-like, and, like other intermediate filaments, can recover a significant portion of their network elasticity after shear. The assembly efficiency of crescentin is largely unaffected by monovalent cations (K(+, Na(+, but is enhanced by divalent cations (Mg(2+, Ca(2+, suggesting that the assembly kinetics and micromechanics of crescentin depend on the valence of the ions present in solution. CONCLUSIONS/SIGNIFICANCE: These results indicate that crescentin forms filamentous structures that are elastic, labile, and stiff, and that their low dissociation rate from established structures controls the slow remodeling of crescentin in C. crescentus.

  8. Nicotine activates the chemosensory cation channel TRPA1. (United States)

    Talavera, Karel; Gees, Maarten; Karashima, Yuji; Meseguer, Víctor M; Vanoirbeek, Jeroen A J; Damann, Nils; Everaerts, Wouter; Benoit, Melissa; Janssens, Annelies; Vennekens, Rudi; Viana, Félix; Nemery, Benoit; Nilius, Bernd; Voets, Thomas


    Topical application of nicotine, as used in nicotine replacement therapies, causes irritation of the mucosa and skin. This reaction has been attributed to activation of nicotinic acetylcholine receptors (nAChRs) in chemosensory neurons. In contrast with this view, we found that the chemosensory cation channel transient receptor potential A1 (TRPA1) is crucially involved in nicotine-induced irritation. We found that micromolar concentrations of nicotine activated heterologously expressed mouse and human TRPA1. Nicotine acted in a membrane-delimited manner, stabilizing the open state(s) and destabilizing the closed state(s) of the channel. In the presence of the general nAChR blocker hexamethonium, nociceptive neurons showed nicotine-induced responses that were strongly reduced in TRPA1-deficient mice. Finally, TRPA1 mediated the mouse airway constriction reflex to nasal instillation of nicotine. The identification of TRPA1 as a nicotine target suggests that existing models of nicotine-induced irritation should be revised and may facilitate the development of smoking cessation therapies with less adverse effects.

  9. Nature as a source of inspiration for cationic lipid synthesis. (United States)

    Labas, Romain; Beilvert, Fanny; Barteau, Benoit; David, Stéphanie; Chèvre, Raphaël; Pitard, Bruno


    Synthetic gene delivery systems represent an attractive alternative to viral vectors for DNA transfection. Cationic lipids are one of the most widely used non-viral vectors for the delivery of DNA into cultured cells and are easily synthesized, leading to a large variety of well-characterized molecules. This review discusses strategies for the design of efficient cationic lipids that overcome the critical barriers of in vitro transfection. A particular focus is placed on natural hydrophilic headgroups and lipophilic tails that have been used to synthesize biocompatible and non-toxic cationic lipids. We also present chemical features that have been investigated to enhance the transfection efficiency of cationic lipids by promoting the escape of lipoplexes from the endosomal compartment and DNA release from DNA-liposome complexes. Transfection efficiency studies using these strategies are likely to improve the understanding of the mechanism of cationic lipid-mediated gene delivery and to help the rational design of novel cationic lipids.

  10. Ensuring Stability

    Institute of Scientific and Technical Information of China (English)


    "Stable"will be a key word for China’s economy in 2012.That’s the beat set at the annual Central Economic Work Conference held in Beijing on December 12-14,which reviewed this year’s development and mapped out plans for the next year.Policymakers at the conference decided to keep macroeconomic policies stable,seek a stable and relatively fast economic growth,stabilize consumer prices and maintain social stability in 2012.On the basis of stability,the government will transform the development model,deepen reform and improve people’s livelihood.

  11. Non-bonding interactions and non-covalent delocalization effects play a critical role in the relative stability of group 12 complexes arising from interaction of diethanoldithiocarbamate with the cations of transition metals Zn(II), Cd(II), and Hg(II): a theoretical study. (United States)

    Bahrami, Homayoon; Farhadi, Saeed; Siadatnasab, Firouzeh


    The chelating properties of diethanoldithiocarbamate (DEDC) and π-electron flow from the nitrogen atom to the sulfur atom via a plane-delocalized π-orbital system (quasi ring) was studied using a density functional theory method. The molecular structure of DEDC and its complexes with Zn(II), Cd(II), and Hg(II) were also considered. First, the geometries of this ligand and DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) were optimized, and the formation energies of these complexes were then calculated based on the electronic energy, or sum of electronic energies, with the zero point energy of each species. Formation energies indicated the DEDC-Zn(II) complex as the most stable complex, and DEDC-Cd(II) as the least stable. Structural data showed that the N1-C2 π-bond was localized in the complexes rather than the ligand, and a delocalized π-bond over S7-C2-S8 was also present. The stability of DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) complexes increased in the presence of the non-specific effects of the solvent (PCM model), and their relative stability did not change. There was π-electron flow or resonance along N1-C2-S7 and along S7-C2-S8 in the ligand. The π-electron flow or resonance along N1-C2-S7 was abolished when the metal interacted with sulfur atoms. Energy belonging to van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand was calculated for each complex. The results of nucleus-independent chemical shift (NICS) indicated a decreasing trend as Zn(II) < Cd(II) < Hg(II) for the aromaticity of the quasi-rings. Finally, by ignoring van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand, the relative stability of the complexes was changed as follows:[Formula: see text] Graphical Abstract Huge electronic cloud localized on Hg(II) in the Hg(II)-DEDC complex.

  12. Stabilizing Niger

    DEFF Research Database (Denmark)

    Hahonou, Eric Komlavi

    international intervention in Niger. Their main objective is to secure their own strategic, economic and political interests by strengthening the Nigerien authorities through direct intervention and capacity building activities. For western states reinforcing state security institutions and stabilizing elite...

  13. Optimizing delivery systems for cationic biopolymers: competitive interactions of cationic polylysine with anionic κ-carrageenan and pectin. (United States)

    Lopez-Pena, Cynthia Lyliam; McClements, David Julian


    Polylysine is a cationic biopolymer with a strong antimicrobial activity against a wide range of microorganisms, however, its functional performance is influenced by its interactions with anionic biopolymers. We examined the stability of polylysine-pectin complexes in the presence of carrageenan, and vice versa. Polylysine-pectin or polylysine-carrageenan complexes were formed at mass ratios of 1:0 to 1:32 (pH 3.5), and then micro-electrophoresis, turbidity, microscopy, and isothermal titration calorimetry (ITC) were used to characterise them. Solutions containing polylysine-pectin complexes were slightly turbid and relatively stable to aggregation at high mass ratios, whereas those containing polylysine-carrageenan complexes were turbid and unstable to aggregation and precipitation. Pectin did not strongly interact with polylysine-carrageenan complexes, whereas carrageenan displaced pectin from polylysine-pectin complexes, which was attributed to differences in electrostatic attraction between polylysine, carrageenan, and pectin. These results have important implications for the design of effective antimicrobial delivery systems for foods and beverages.

  14. Partially folded intermediates during trypsinogen denaturation

    Directory of Open Access Journals (Sweden)

    Martins N.F.


    Full Text Available The equilibrium unfolding of bovine trypsinogen was studied by circular dichroism, differential spectra and size exclusion HPLC. The change in free energy of denaturation was = 6.99 ± 1.40 kcal/mol for guanidine hydrochloride and = 6.37 ± 0.57 kcal/mol for urea. Satisfactory fits of equilibrium unfolding transitions required a three-state model involving an intermediate in addition to the native and unfolded forms. Size exclusion HPLC allowed the detection of an intermediate population of trypsinogen whose Stokes radii varied from 24.1 ± 0.4 Å to 26.0 ± 0.3 Å for 1.5 M and 2.5 M guanidine hydrochloride, respectively. During urea denaturation, the range of Stokes radii varied from 23.9 ± 0.3 Å to 25.7 ± 0.6 Å for 4.0 M and 6.0 M urea, respectively. Maximal intrinsic fluorescence was observed at about 3.8 M urea with 8-aniline-1-naphthalene sulfonate (ANS binding. These experimental data indicate that the unfolding of bovine trypsinogen is not a simple transition and suggest that the equilibrium intermediate population comprises one intermediate that may be characterized as a molten globule. To obtain further insight by studying intermediates representing different stages of unfolding, we hope to gain a better understanding of the complex interrelations between protein conformation and energetics.

  15. A Balancing Act: Stability versus Reactivity of Mn(O) Complexes. (United States)

    Neu, Heather M; Baglia, Regina A; Goldberg, David P


    A large class of heme and non-heme metalloenzymes utilize O2 or its derivatives (e.g., H2O2) to generate high-valent metal-oxo intermediates for performing challenging and selective oxidations. Due to their reactive nature, these intermediates are often short-lived and very difficult to characterize. Synthetic chemists have sought to prepare analogous metal-oxo complexes with ligands that impart enough stability to allow for their characterization and an examination of their inherent reactivity. The challenge in designing these molecules is to achieve a balance between their stability, which should allow for their in situ characterization or isolation, and their reactivity, in which they can still participate in interesting chemical transformations. This Account focuses on our recent efforts to generate and stabilize high-valent manganese-oxo porphyrinoid complexes and tune their reactivity in the oxidation of organic substrates. Dioxygen can be used to generate a high-valent Mn(V)(O) corrolazine (Mn(V)(O)(TBP8Cz)) by irradiation of Mn(III)(TBP8Cz) with visible light in the presence of a C-H substrate. Quantitative formation of the Mn(V)(O) complex occurs with concomitant selective hydroxylation of the benzylic substrate hexamethylbenzene. Addition of a strong H(+) donor converted this light/O2/substrate reaction from a stoichiometric to a catalytic process with modest turnovers. The addition of H(+) likely activates a transient Mn(V)(O) complex to achieve turnover, whereas in the absence of H(+), the Mn(V)(O) complex is an unreactive "dead-end" complex. Addition of anionic donors to the Mn(V)(O) complex also leads to enhanced reactivity, with a large increase in the rate of two-electron oxygen atom transfer (OAT) to thioether substrates. Spectroscopic characterization (Mn K-edge X-ray absorption and resonance Raman spectroscopies) revealed that the anionic donors (X(-)) bind to the Mn(V) ion to form six-coordinate [Mn(V)(O)(X)](-) complexes. An unusual "V

  16. Investigations on the liquid crystalline phases of cation-induced condensed DNA

    Indian Academy of Sciences (India)

    C K S Pillai; Neethu Sundaresan; M Radhakrishnan Pillai; T Thomas; T J Thomas


    Viral and nonviral condensing agents are used in gene therapy to compact oligonucleotides and plasmid DNA into nanostructures for their efficient transport through the cell membranes. Whereas viral vectors are best by the toxic effects on the immune system, most of the nonviral delivery vehicles are not effective for use in clinical system. Recent investigations indicate that the supramolecular organization of DNA in the condensed state is liquid crystalline. The present level of understanding of the liquid crystalline phase of DNA is inadequate and a thorough investigation is required to understand the nature, stability, texture and the influence of various environmental conditions on the structure of the phase. The present study is mainly concerned with the physicochemical investigations on the liquid crystalline transitions during compaction of DNA by cationic species such as polyamines and metallic cations. As a preliminary to the above investigation, studies were conducted on the evolution of mesophase transitions of DNA with various cationic counterion species using polarized light microscopy. These studies indicated significant variations in the phase behaviour of DNA in the presence of Li and other ions. Apart from the neutralization of the charges on the DNA molecule, these ions are found to influence selectively the hydration sphere of DNA that in turn influences the induction and stabilization of the LC phases. The higher stability observed with the liquid crystalline phases of Li-DNA system could be useful in the production of nanostructured DNA. In the case of the polyamine, a structural specificity effect depending on the nature, charge and structure of the polyamine used has been found to be favoured in the crystallization of DNA.

  17. Spectroscopy and computational studies on the interaction of octyl, dodecyl, and hexadecyl derivatives of anionic and cationic surfactants with adenosine deaminase. (United States)

    Ajloo, Davood; Mahmoodabadi, Najmeh; Ghadamgahi, Maryam; Saboury, Ali Akbar


    Effects of sodium (octyl, dodecyl, hexadecyl) sulfate and their cationic analogous on the structure of adenosine deaminase (ADA) were investigated by fluorescence and circular dichroism spectroscopy as well as molecular dynamics simulation and docking calculation. Root-mean-square derivations, radius of gyration, solvent accessible surface area, and radial distribution function were obtained. The results showed that anionic and cationic surfactants reduce protein stability. Cationic surfactants have more effect on the ADA structure in comparison with anionic surfactants. More concentration and longer surfactants are parallel to higher denaturation. Furthermore, aggregation in the presence of anionic surfactants is more than cationic surfactants. Docking data showed that longer surfactants have more interaction energy and smaller ones bound to the active site.

  18. Cation-π interaction of the univalent silver cation with meso-octamethylcalix[4]pyrrole: Experimental and theoretical study (United States)

    Polášek, Miroslav; Kvíčala, Jaroslav; Makrlík, Emanuel; Křížová, Věra; Vaňura, Petr


    By using electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent silver cation Ag+ forms with meso-octamethylcalix[4]pyrrole (abbrev. 1) the cationic complex species 1·Ag+. Further, applying quantum chemical DFT calculations, four different conformations of the resulting complex 1·Ag+ were derived. It means that under the present experimental conditions, this ligand 1 can be considered as a macrocyclic receptor for the silver cation.

  19. Capturing dynamic cation hopping in cubic pyrochlores (United States)

    Brooks Hinojosa, Beverly; Asthagiri, Aravind; Nino, Juan C.


    In direct contrast to recent reports, density functional theory predicts that the most stable structure of Bi2Ti2O7 pyrochlore is a cubic Fd3¯m space group by accounting for atomic displacements. The displaced Bi occupies the 96g(x,x,z) Wyckoff position with six equivalent sites, which create multiple local minima. Using nudged elastic band method, the transition states of Bi cation hopping between equivalent minima were investigated and an energy barrier between 0.11 and 0.21 eV was determined. Energy barriers associated with the motion of Bi between equivalent sites within the 96g Wyckoff position suggest the presence of dielectric relaxation in Bi2Ti2O7.

  20. Retention of Cationic Starch onto Cellulose Fibres (United States)

    Missaoui, Mohamed; Mauret, Evelyne; Belgacem, Mohamed Naceur


    Three methods of cationic starch titration were used to quantify its retention on cellulose fibres, namely: (i) the complexation of CS with iodine and measurement of the absorbency of the ensuing blue solution by UV-vis spectroscopy; (ii) hydrolysis of the starch macromolecules followed by the conversion of the resulting sugars to furan-based molecules and quantifying the ensuing mixture by measuring their absorbance at a Ι of 490 nm, using the same technique as previous one and; finally (iii) hydrolysis of starch macromolecules by trifluoro-acetic acid and quantification of the sugars in the resulting hydrolysates by high performance liquid chromatography. The three methods were found to give similar results within the range of CS addition from 0 to 50 mg per g of cellulose fibres.

  1. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    DEFF Research Database (Denmark)

    Ellegaard, Anne-Marie; Dehlendorff, Christian; Vind, Anna C.;


    Non-small cell lung cancer (NSCLC) is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD) library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We...... then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients...... with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any...

  2. Heart imaging with cationic complexes of technetium

    Energy Technology Data Exchange (ETDEWEB)

    Deutsch, E. (Univ. of Cincinnati, Cincinnati, OH); Bushong, W.; Glavan, K.A.; Elder, R.C.; Sodd, V.J.; Scholz, K.L.; Fortman, D.L.; Lukes, S.J.


    The cationic technetium-99 complex trans-(/sup 99/Tc(dmpe)/sub 2/Cl/sub 2/)/sup +/, where dmpe is bis(1,2-dimethylphosphino)ethane or (CH/sub 3/)/sub 2/P-CH/sub 2/CH/sub 2/-P(CH/sub 3/)/sub 2/, has been prepared and characterized by single-crystal, x-ray structural analysis. The technetium-99m analog, trans-(/sup 99m/Tc (dmpe)/sub 2/Cl/sub 2/)/sup +/, has also been prepared and shown to yield excellent gamma-ray images of the heart. The purposeful design, characterization, and synthesis of this technetium-99m radiopharmaceutical represents a striking application of fundamental inorganic chemistry to a problem in applied nuclear medicine.

  3. Electron spectra of radical cations of heteroanalogs

    Energy Technology Data Exchange (ETDEWEB)

    Petrushenko, K.B.; Turchaninov, V.K.; Vokin, A.I.; Ermikov, A.F.; Frolov, Yu.L.


    Radical cation spectra of indazole and benzothiophene in the visible region were obtained by laser photolysis during the reaction of photoexcited quinones with these compounds in acetonitrile. The charge transfer bands of the complexes of the test compounds with p-chloranil and 7,7,8,8-tetracyanoquinodimethane in dioxane were recorded on a Specord M-40. Photoelectron spectra were obtained on a ES-3201 electron spectrometer. The He(I) resonance band (21.21 eV) was used for excitation. Measurements were carried out in the 60-120/sup 0/C range. The energy scale was calibrated form the first ionization potentials of Ar (15.76 eV) and chlorobenzene (9.06 eV). The error in the determination of the ionization potentials for the first four photoelectron bands was 0.05 eV.

  4. Hydration Structure of the Quaternary Ammonium Cations

    KAUST Repository

    Babiaczyk, Wojtek Iwo


    Two indicators of the hydropathicity of small solutes are introduced and tested by molecular dynamics simulations. These indicators are defined as probabilities of the orientation of water molecules\\' dipoles and hydrogen bond vectors, conditional on a generalized distance from the solute suitable for arbitrarily shaped molecules. Using conditional probabilities, it is possible to distinguish features of the distributions in close proximity of the solute. These regions contain the most significant information on the hydration structure but cannot be adequately represented by using, as is usually done, joint distance-angle probability densities. Our calculations show that using our indicators a relative hydropathicity scale for the interesting test set of the quaternary ammonium cations can be roughly determined. © 2010 American Chemical Society.

  5. Switching between dynamic states in intermediate-length Josephson junctions

    DEFF Research Database (Denmark)

    Pagano, S.; Sørensen, Mads Peter; Parmentier, R. D.


    The appearance of zero-field steps (ZFS’s) in the current-voltage characteristics of intermediate-length overlap-geometry Josephson tunnel junctions described by a perturbed sine-Gordon equation (PSGE) is associated with the growth of parametrically excited instabilities of the McCumber background...... curve (MCB). A linear stability analysis of a McCumber solution of the PSGE in the asymptotic linear region of the MCB and in the absence of magnetic field yields a Hill’s equation which predicts how the number, locations, and widths of the instability regions depend on the junction parameters....... A numerical integration of the PSGE in terms of truncated series of time-dependent Fourier spatial modes verifies that the parametrically excited instabilities of the MCB evolve into the fluxon oscillations characteristic of the ZFS’s. An approximate analysis of the Fourier mode equations in the presence...

  6. Emergence and transmission of arbovirus evolutionary intermediates with epidemic potential. (United States)

    Stapleford, Kenneth A; Coffey, Lark L; Lay, Sreyrath; Bordería, Antonio V; Duong, Veasna; Isakov, Ofer; Rozen-Gagnon, Kathryn; Arias-Goeta, Camilo; Blanc, Hervé; Beaucourt, Stéphanie; Haliloğlu, Türkan; Schmitt, Christine; Bonne, Isabelle; Ben-Tal, Nir; Shomron, Noam; Failloux, Anna-Bella; Buchy, Philippe; Vignuzzi, Marco


    The high replication and mutation rates of RNA viruses can result in the emergence of new epidemic variants. Thus, the ability to follow host-specific evolutionary trajectories of viruses is essential to predict and prevent epidemics. By studying the spatial and temporal evolution of chikungunya virus during natural transmission between mosquitoes and mammals, we have identified viral evolutionary intermediates prior to emergence. Analysis of virus populations at anatomical barriers revealed that the mosquito midgut and salivary gland pose population bottlenecks. By focusing on virus subpopulations in the saliva of multiple mosquito strains, we recapitulated the emergence of a recent epidemic strain of chikungunya and identified E1 glycoprotein mutations with potential to emerge in the future. These mutations confer fitness advantages in mosquito and mammalian hosts by altering virion stability and fusogenic activity. Thus, virus evolutionary trajectories can be predicted and studied in the short term before new variants displace currently circulating strains.

  7. Outflow forces in intermediate mass star formation

    CERN Document Server

    van Kempen, T A; van Dishoeck, E F; Kristensen, L E; Belloche, A; Klaassen, P D; Leurini, S; Jose-Garcia, I San; Aykutalp, A; Choi, Y; Endo, A; Frieswijk, W; Harsono, D; Karska, A; Koumpia, E; van der Marel, N; Nagy, Z; Perez-Beaupuits, J P; Risacher, C; van Weeren, R J; Wyrowski, F; Yildiz, U A; Guesten, R; Boland, W; Baryshev, A


    Intermediate mass protostarsprovide a bridge between theories of low- and high-mass star formation. Emerging molecular outflows can be used to determine the influence of fragmentation and multiplicity on protostellar evolution through the correlation of outflow forces of intermediate mass protostars with the luminosity. The aim of this paper is to derive outflow forces from outflows of six intermediate mass protostellar regions and validate the apparent correlation between total luminosity and outflow force seen in earlier work, as well as remove uncertainties caused by different methodology. By comparing CO 6--5 observations obtained with APEX with non-LTE radiative transfer model predictions, optical depths, temperatures, densities of the gas of the molecular outflows are derived. Outflow forces, dynamical timescales and kinetic luminosities are subsequently calculated. Outflow parameters, including the forces, were derived for all sources. Temperatures in excess of 50 K were found for all flows, in line wi...

  8. The ARES High-level Intermediate Representation

    Energy Technology Data Exchange (ETDEWEB)

    Moss, Nicholas David [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    The LLVM intermediate representation (IR) lacks semantic constructs for depicting common high-performance operations such as parallel and concurrent execution, communication and synchronization. Currently, representing such semantics in LLVM requires either extending the intermediate form (a signi cant undertaking) or the use of ad hoc indirect means such as encoding them as intrinsics and/or the use of metadata constructs. In this paper we discuss a work in progress to explore the design and implementation of a new compilation stage and associated high-level intermediate form that is placed between the abstract syntax tree and when it is lowered to LLVM's IR. This highlevel representation is a superset of LLVM IR and supports the direct representation of these common parallel computing constructs along with the infrastructure for supporting analysis and transformation passes on this representation.

  9. Magnetic Resonance Studies of Proton Loss from Carotenoid Radical Cations

    Energy Technology Data Exchange (ETDEWEB)

    Kispert, Lowell D [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Focsan, A Ligia [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Konovalova, Tatyana A [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence, Jesse [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Bowman, Michael K [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Molnar, Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Deli, Jozsef [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)


    Carotenoids, intrinsic components of reaction centers and pigment-protein complexes in photosynthetic membranes, play a photoprotective role and serve as a secondary electron donor. Before optimum use of carotenoids can be made in artificial photosynthetic systems, their robust nature in living materials requires extensive characterization of their electron transfer, radical trapping ability, stability, structure in and on various hosts, and photochemical behavior. Pulsed ENDOR and 2D-HYSCORE studies combined with DFT calculations reveal that photo-oxidation of natural zeaxanthin (I) and violaxanthin (II) on silica-alumina produces not only the carotenoid radical cations (Car•+) but also neutral radicals (#Car•) by proton loss from the methyl groups at positions 5 or 5', and possibly 9 or 9' and 13 or 13'. Notably, the proton loss favored in I at the 5 position by DFT calculations, is unfavorable in II due to the epoxide at the 5, 6 position. DFT calculations predict the isotropic methyl proton couplings of 8-10 MHz for Car•+ which agree with the ENDOR for carotenoid α-conjugated radical cations. Large α-proton hyperfine coupling constants (>10 MHz) determined from HYSCORE are assigned from the DFT calculations to neutral carotenoid radicals. Proton loss upon photolysis was also examined as a function of carotenoid polarity [Lycopene (III) versus 8'-apo-β-caroten-8'-al (IV)]; hydrogen bonding [Lutein (V) versus III]; host [silica-alumina versus MCM-41 molecular sieve]; and substituted metal in MCM-41. Loss of H+ from the 5(5'), 9(9') or 13(13') methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1Ch1* decays via energy transfer to the carotenoid which returns to the ground state by thermal dissipation; or via electron transfer to form a charge transfer state (I •+…Chl•-), lower in energy than 1Chl*. Formation of I •+ results in bond

  10. Antiviral effect of cationic compounds on bacteriophages

    Directory of Open Access Journals (Sweden)

    Mai Huong eChatain-Ly


    Full Text Available The antiviral activity of several cationic compounds - cetytrimethylammonium (CTAB, chitosan, nisin and lysozyme - was investigated on the bacteriophage c2 (DNA head and non-contractile tail infecting Lactococcus strains and the bacteriophage MS2 (F-specific RNA infecting E.coli. Firstly, these activities were evaluated in a phosphate buffer pH 7- 10 mM. The CTAB had a virucidal effect on the Lactococcus bacteriophages, but not on the MS2. After 1 min of contact with 0.125 mM CTAB, the c2 population was reduced from 6 log(pfu/mL to 1,5 log(pfu/mL and completely deactivated at 1 mM. On the contrary, chitosan inhibited the MS2 more than it did the bacteriophages c2. No antiviral effect was observed for the nisin or the lysozyme on bacteriophages after 1 min of treatment. A 1 and 2.5 log reduction was respectively observed for nisin and lysozyme when the treatment time increased (5 or 10 min. These results showed that the antiviral effect depended both on the virus and structure of the antimicrobial compounds. The antiviral activity of these compounds was also evaluated in different physico-chemical conditions and in complex matrices. The antiviral activity of CTAB was impaired in acid pH and with an increase of the ionic strength. These results might be explained by the electrostatic interactions between cationic compounds and negatively charged particles such as bacteriophages or other compounds in a matrix. Milk proved to be protective suggesting the components of food could interfere with antimicrobial compounds.

  11. Refolding of Denatured/Reduced Lysozyme Using Weak-Cation Exchange Chromatography

    Institute of Scientific and Technical Information of China (English)

    Yan WANG; Bo Lin GONG; Xin Du GENG


    Oxidative refolding of the denatured/reduced lysozyme was investigated by using weak-cation exchange chromatography (WCX). The stationary phase of WCX binds to the reduced lysozyme and prevented it from forming intermolecular aggregates. At the same time urea and ammonium sulfate were added to the mobile phase to increase the elution strength for lysozyme. Ammonium sulfate can more stabilize the native protein than a common eluting agent, sodium chloride. Refolding of lysozyme by using this WCX is successfully. It was simply carried out to obtain a completely and correctly refolding of the denatured lysozyme at high concentration of 20.0 mg/mL.

  12. Synthesis and Characterization of Yttrium Doped Nano-zirconia by a Cationic Surfactant-assisted Route

    Institute of Scientific and Technical Information of China (English)

    YU Jian-Chang; HU Shen-Wei


    Recently, more and more interest has been focused on zirconia for its unique characteristics. In this paper, via the preceding preparation technique, yttrium can be successfully incorporated into nano-zirconia by a cationic surfactant-assisted route. The methods of XRD, TEM, EDS, Uv-vis and N2 adsorption-desorption are adopted to characterize the synthesized samples. The results show that the yttrium has been successfully incorporated into the zirconia lattice, and the thermal stability of yttrium doped zirconia has been enhanced remarkably.

  13. Impact of cationic diffusion on properties of iron-bearing glass fibres

    DEFF Research Database (Denmark)

    Smedskjaer, Morten M.; Yue, Yuanzheng; Deubener, Joachim;


    A silica-rich surface layer of Fe3+-containing aluminosilicate glass fibres is created by means of an inward diffusion process of divalent network modifying cations. The latter is caused by the reduction of Fe3+ to Fe2+ when the fibres undergo a heat treatment at temperatures around the glass...... transition temperature (Tg) in a reducing H2/N2 atmosphere. The thickness of the surface layer can be adjusted by varying the temperature or the duration of the heat treatment. The reduction process has a significant impact on the glass transition and crystallization behaviour, high temperature stability...

  14. Role of extracellular cations in cell motility, polarity, and chemotaxis

    Directory of Open Access Journals (Sweden)

    Soll D


    Full Text Available David R Soll1, Deborah Wessels1, Daniel F Lusche1, Spencer Kuhl1, Amanda Scherer1, Shawna Grimm1,21Monoclonal Antibody Research Institute, Developmental Studies, Hybridoma Bank, Department of Biology, University of Iowa, Iowa City; 2Mercy Medical Center, Surgical Residency Program, Des Moines, Iowa, USAAbstract: The concentration of cations in the aqueous environment of free living organisms and cells within the human body influence motility, shape, and chemotaxis. The role of extracellular cations is usually perceived to be the source for intracellular cations in the process of homeostasis. The role of surface molecules that interact with extracellular cations is believed to be that of channels, transporters, and exchangers. However, the role of Ca2+ as a signal and chemoattractant and the discovery of the Ca2+ receptor have demonstrated that extracellular cations can function as signals at the cell surface, and the plasma membrane molecules they interact with can function as bona fide receptors that activate coupled signal transduction pathways, associated molecules in the plasma membrane, or the cytoskeleton. With this perspective in mind, we have reviewed the cationic composition of aqueous environments of free living cells and cells that move in multicellular organisms, most notably humans, the range of molecules interacting with cations at the cell surface, the concept of a cell surface cation receptor, and the roles extracellular cations and plasma membrane proteins that interact with them play in the regulation of motility, shape, and chemotaxis. Hopefully, the perspective of this review will increase awareness of the roles extracellular cations play and the possibility that many of the plasma membrane proteins that interact with them could also play roles as receptors.Keywords: extracellular cations, chemotaxis, transporters, calcium, receptors

  15. Influence of Sulfonated-Kaolin On Cationic Exchange Capacity Swelling Degree and Morphology of Chitosan/Kaolin Composites

    Directory of Open Access Journals (Sweden)

    Ozi Adi Saputra


    Full Text Available Preparation of sulfonated-kaolin (sKao has been conducted and used as filler on chitosan matrix via solution casting method, namely chitosan/sKao (Cs/sKao. Swelling degree, cationic exchange capacity and thermal stability were evaluated to determine chitosan/sKao membranes performance as proton exchange membrane in fuel cell. Functional group analysis of chitosan, sKao and synthesized products were studied using Fourier Transform Infra-Red (FTIR spectroscopy. In this study, swelling degree and swelling area of Cs/sKao are also studied to determine of membrane ability to swelling which compare to unmodified chitosan/kaolin (Cs/Kao. The presence of sKao in chitosan matrix was able to improve cationic exchange capacity (CEC which proved by morphological study of membrane surface after CEC test. Moreover, Thermal stability of Cs/sKao showed the membrane has meet requirement for PEM application.

  16. Blue outliers among intermediate redshift quasars

    CERN Document Server

    Marziani, P; Stirpe, G M; Dultzin, D; Del Olmo, A; Martínez-Carballo, M A


    [Oiii]{\\lambda}{\\lambda}4959,5007 "blue outliers" -- that are suggestive of outflows in the narrow line region of quasars -- appear to be much more common at intermediate z (high luminosity) than at low z. About 40% of quasars in a Hamburg ESO intermediate-z sample of 52 sources qualify as blue outliers (i.e., quasars with [OIII] {\\lambda}{\\lambda}4959,5007 lines showing large systematic blueshifts with respect to rest frame). We discuss major findings on what has become an intriguing field in active galactic nuclei research and stress the relevance of blue outliers to feedback and host galaxy evolution.

  17. Governance-Default Risk Relationship and the Demand for Intermediated and Non-Intermediated Debt

    Directory of Open Access Journals (Sweden)

    Husam Aldamen


    Full Text Available This paper explores the impact of corporate governance on the demand for intermediated debt (asset finance, bank debt, non-bank private debt and non-intermediated debt (public debt in the Australian debt market. Relative to other countries the Australian debt market is characterised by higher proportions of intermediated or private debt with a lower inherent level of information asymmetry in that private lenders have greater access to financial information (Gray, Koh & Tong 2009. Our firm level, cross-sectional evidence suggests that higher corporate governance impacts demand for debt via the mitigation of default risk. However, this relationship is not uniform across all debt types. Intermediated debt such as bank and asset finance debt are more responsive to changes in governance-default risk relationship than non-bank and non-intermediated debt. The implication is that a firm’s demand for different debt types will reflect its governance-default risk profile.

  18. The Effect of Hydration on the Cation-π Interaction Between Benzene and Various Cations

    Indian Academy of Sciences (India)



    The effect of hydration on cation-π interaction in Mq+ BmWn (B = benzene; W = water; Mq+ =Na⁺, K⁺, Mg²⁺, Ca²⁺, Al³⁺, 0 ≤ n,m ≤ 4, 1≤ m + n ≤ 4) complexes has been investigated using ab initio quantum chemical methods. Interaction energy values computed at the MP2 level of theory using the 6-31G(d,p) basis set reveal a qualitative trend in the relative affinity of different cations for benzene and water in these complexes. The π–cloud thickness values for benzene have also been estimated for these systems.

  19. Strontium isotopes provide clues for a process shift in base cation dynamics in young volcanic soils (United States)

    Bingham, N.; Jackson, M. G.; Bookhagen, B.; Maher, K.; Chadwick, O.


    Despite advances in soil development theory based on studies of old soils or over long timescales, little is known about soil thresholds (dramatic changes in soil properties associated with only small shifts in external forcing factors) that might be expressed in young soils (less than 10 kyr). Therefore, we seek to understand infant soil development in a tropical environment through the sourcing of plant available base cations by measuring the strontium (Sr) isotopic composition of the soil exchange complex. Our sampling strategy spans soils in three different precipitation ranges (950-1060 mm, 1180-1210 mm, and 1450-1500) and an array of soil ages from 500 to 7500 years in the Kona region on the island of Hawaii. In Hawaiian soils, 87Sr/86Sr values are determined by a mixture of three components: a mantle-derived component from the lava (0.7034), a rainfall component (0.7093) and a component from continental dust (0.720). Elevation-controlled leaching intensity in the wettest localities produces a decline in the concentration of base cations supplied by basalt and a dilute resupply by rainfall. In the driest sites, where leaching intensity is dramatically reduced, there is a buildup of rainfall-derived extractable Sr in the soil over time. Slow rock weathering rates produce a small rock-derived cation input to the soil. Thus, Sr isotope signatures reflect both the input of rainfall-derived cations and rock-derived cations with values that fall between rainfall and basaltic signatures. Soils in the intermediate precipitation range have Sr isotopic signatures consistent with both the wet and dry trends; suggesting that they lie close to the critical precipitation amount that marks a shift between these two processes. For the Kona region, this transition seems to occur at 1200 mm /yr. In contrast to the clear-cut differentiation in strontium isotopes with precipitation shifts observed in older soils, patterns on these young soils in Kona are complicated by low soil

  20. Chiroptical properties of cation complexes of chiral phenazino-18-crown-6 ether-type hosts. (United States)

    Szarvas, Szilvia; Szalay, Luca; Vass, Elemér; Hollósi, Miklós; Samu, Erika; Huszthy, Péter


    Herein we report CD spectroscopic studies on complexes of (R,R)-dimethyl-, (R,R)-diisobutyl-, and (S,S)-di-sec-butyl-phenazino-18-crown-6 ligands (Scheme 1) with selected alkali (Na+, K+), alkaline earth (Mg2+, Ca2+), and transition-metal (Ag+, Zn2+, Ni2+, Cd2+, Pb2+) cations. The complexation was monitored in the 300- to 240-nm region of the CD spectra comprising mainly the 1Bb band of the heteroaromatic subunit. The CD spectra of the complexes showed an unexpected diversity. In the most characteristic 1Bb spectral region, the number, position, and intensity of band(s) depend not only on the heteroaromatic subunit and the size of the substituents but also on the diameter, ion strength, and coordination geometry of the cation. The appearance of two weak 1Bb CD bands (type-I spectra) with the sign pattern of the host is an indication of two complexes of comparable stability. The "type-II" spectra differ from that of the host in the number, sign pattern, and intensity of the bands. Complexes of transition-metal cations generally show CD spectra with more intense bands. The CD spectra of complexes of (S,S)-di-sec-butyl-phenazino-18-crown-6 ligand with Na+, K+, and Pb2+ (type III) strongly suggest exciton coupling caused by the closeness of the heteroaromatic rings of two 1:1 complex molecules.

  1. The interdigitated gel phase in mixtures of cationic and zwitterionic phospholipids. (United States)

    Smith, Eric A; Dea, Phoebe K


    To examine the phase behavior of mixtures of zwitterionic and cationic lipids we used three derivatives of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). All three lipids are uniquely capable of spontaneously forming the interdigitated gel phase (LβI) under typical hydration conditions. The P-O-ethyl derivative, 1,2-dipalmitoyl-sn-glycero-3-ethylphosphocholine (EDPPC), was chosen as the cationic lipid. For the zwitterionic lipids, we use the ether-linked 1,2-di-O-hexadecyl-sn-glycero-3-phosphocholine, (DHPC) and the fluorine substituted 1-palmitoyl-2-(16-fluoropalmitoyl)-sn-glycero-3-phosphocholine (F-DPPC). Differential scanning calorimetry (DSC) and fluorescence spectroscopy were used to analyze the lipid mixtures. The F-DPPC/EDPPC mixtures are interdigitated at all lipid ratios below the main transition temperature (Tm). In addition, EDPPC stabilizes the interdigitated gel phase of DHPC until the ripple gel phase (Pβ') is eliminated and only the LβI to liquid crystalline phase (Lα) main transition remains. These results demonstrate that mixtures of cationic and zwitterionic lipids can be compatible with the interdigitated phase.

  2. Efficient Removal of Cationic and Anionic Radioactive Pollutants from Water Using Hydrotalcite-Based Getters. (United States)

    Bo, Arixin; Sarina, Sarina; Liu, Hongwei; Zheng, Zhanfeng; Xiao, Qi; Gu, Yuantong; Ayoko, Godwin A; Zhu, Huaiyong


    Hydrotalcite (HT)-based materials are usually applied to capture anionic pollutants in aqueous solutions. Generally considered anion exchangers, their ability to capture radioactive cations is rarely exploited. In the present work, we explored the ability of pristine and calcined HT getters to effectively capture radioactive cations (Sr(2+) and Ba(2+)) which can be securely stabilized at the getter surface. It is found that calcined HT outperforms its pristine counterpart in cation removal ability. Meanwhile, a novel anion removal mechanism targeting radioactive I(-) is demonstrated. This approach involves HT surface modification with silver species, namely, Ag2CO3 nanoparticles, which can attach firmly on HT surface by forming coherent interface. This HT-based anion getter can be further used to capture I(-) in aqueous solution. The observed I(-) uptake mechanism is distinctly different from the widely reported ion exchange mechanism of HT and much more efficient. As a result of the high local concentrations of precipitants on the getters, radioactive ions in water can be readily immobilized onto the getter surface by forming precipitates. The secured ionic pollutants can be subsequently removed from water by filtration or sedimentation for safe disposal. Overall, these stable, inexpensive getters are the materials of choice for removal of trace ionic pollutants from bulk radioactive liquids, especially during episodic environmental crisis.

  3. Surface-orientation-dependent distribution of subsurface cation-exchange defects in olivine-phosphate nanocrystals. (United States)

    Chung, Sung-Yoon; Choi, Si-Young; Kim, Tae-Hwan; Lee, Seongsu


    Atomic-scale exchange between two different cations of similar size in crystalline oxides is one of the major types of point defects when multiple cations in oxygen interstitials are arrayed in an ordered manner. Although a number of studies have been performed on a variety of Li-intercalation olivine phosphates to determine the distribution of exchange defects in bulk, understanding of the thermodynamic stability of the defects in subsurface regions and its dependency on the crystallographic orientation at the surface has remained elusive. Through a combination of small-angle neutron scattering, atomic-scale direct probing with scanning transmission electron microscopy, and theoretical ab initio calculations, we directly demonstrate that the antisite exchange defects are distributed in a highly anisotropic manner near the surfaces of LiFePO4 crystals. Moreover, a substantial amount of cation exchanges between Li and Fe sites is identified as an energetically favorable configuration in some surface regions, showing excellent agreement with the calculation results of negative defect formation energies. The findings in this study provide insight into developing better ways to avoid degradation of lithium mobility through the surface as well as scientifically notable features regarding the distribution of exchange defects in olivine phosphates.

  4. Chapter 17 - Engineering cationic liposome siRNA complexes for in vitro and in vivo delivery. (United States)

    Podesta, Jennifer E; Kostarelos, Kostas


    RNA interference, the sequence-specific silencing of gene expression by introduction of short interfering RNA (siRNA) is a powerful tool that that the potential to act as a therapeutic agent and the advantage of decreasing toxic effects on normal tissue sometimes seen with conventional treatments i.e. small molecule inhibitors. Naked, unmodified siRNA is poorly taken up by cells and is subject to degradation when exposed to blood proteins during systemic administration. It has also been shown to produce non-specific immune response as well as having the potential to generate 'off-target' effects. Therefore there is a requirement for a delivery system to not only protect the siRNA and facilitate its uptake, but additionally to offer the potential for targeted delivery with an aim of exploiting the high specificity afforded by RNA interference. Cationic liposomes are the most studied, non-viral delivery system used for nucleic acid delivery. As such, the use of cationic liposomes is promising for siRNA for delivery. Furthermore, polyethylene glycol (PEG) can be incorporated into the liposome formulation to create sterically stabilized or 'stealth' liposomes. Addition of PEG can reduce recognition by the reticuloendothelial system (RES) thereby prolonging circulation time. Here we describe a methodology for the complexation of siRNA with cationic liposomes and PEGylated liposomes using two protocols: mixing and encapsulation. Moreover, the different formulations are compared head to head to demonstrate their efficacy for gene silencing.

  5. Kinetic Monte Carlo Simulation of Cation Diffusion in Low-K Ceramics (United States)

    Good, Brian


    Low thermal conductivity (low-K) ceramic materials are of interest to the aerospace community for use as the thermal barrier component of coating systems for turbine engine components. In particular, zirconia-based materials exhibit both low thermal conductivity and structural stability at high temperature, making them suitable for such applications. Because creep is one of the potential failure modes, and because diffusion is a mechanism by which creep takes place, we have performed computer simulations of cation diffusion in a variety of zirconia-based low-K materials. The kinetic Monte Carlo simulation method is an alternative to the more widely known molecular dynamics (MD) method. It is designed to study "infrequent-event" processes, such as diffusion, for which MD simulation can be highly inefficient. We describe the results of kinetic Monte Carlo computer simulations of cation diffusion in several zirconia-based materials, specifically, zirconia doped with Y, Gd, Nb and Yb. Diffusion paths are identified, and migration energy barriers are obtained from density functional calculations and from the literature. We present results on the temperature dependence of the diffusivity, and on the effects of the presence of oxygen vacancies in cation diffusion barrier complexes as well.

  6. Effect of divalent cations on DMPC/DHPC bicelle formation and alignment. (United States)

    Brindley, Amanda J; Martin, Rachel W


    Many important classes of biomolecules require divalent cations for optimal activity, making these ions essential for biologically relevant structural studies. Bicelle mixtures composed of short-chain and long-chain lipids are often used in solution- and solid-state NMR structure determination; however, the phase diagrams of these useful orienting media and membrane mimetics are sensitive to other solution components. Therefore, we have investigated the effect of varying concentrations of four divalent cations, Ca(2+), Mg(2+), Zn(2+), and Cd(2+), on cholesterol sulfate-stabilized DMPC/DHPC bicelles. We found that low concentrations of all the divalent ions are tolerated with minimal perturbation. At higher concentrations Zn(2+) and Cd(2+) disrupt the magnetically aligned phase while Ca(2+) and Mg(2+) produce more strongly oriented phases. This result indicates that divalent cations are not only required to maintain the biological activity of proteins and nucleic acids; they may also be used to manipulate the behavior of the magnetically aligned phase.

  7. In vivo toxicity of cationic micelles and liposomes

    DEFF Research Database (Denmark)

    Knudsen, Kristina Bram; Northeved, Helle; Ek, Pramod Kumar


    This study investigated toxicity of nanocarriers comprised of cationic polymer and lipid components often used in gene and drug delivery, formulated as cationic micelles and liposomes. Rats were injected intravenously with 10, 25 or 100 mg/kg and sacrificed after 24 or 48 h, or 24 h after the last...

  8. How mobile are sorbed cations in clays and clay rocks? (United States)

    Gimmi, T; Kosakowski, G


    Diffusion of cations and other contaminants through clays is of central interest, because clays and clay rocks are widely considered as barrier materials for waste disposal sites. An intriguing experimental observation has been made in this context: Often, the diffusive flux of cations at trace concentrations is much larger and the retardation smaller than expected based on their sorption coefficients. So-called surface diffusion of sorbed cations has been invoked to explain the observations but remains a controversial issue. Moreover, the corresponding surface diffusion coefficients are largely unknown. Here we show that, by an appropriate scaling, published diffusion data covering a broad range of cations, clays, and chemical conditions can all be modeled satisfactorily by a surface diffusion model. The average mobility of sorbed cations seems to be primarily an intrinsic property of each cation that follows inversely its sorption affinity. With these surface mobilities, cation diffusion coefficients can now be estimated from those of water tracers. In pure clays at low salinities, surface diffusion can reduce the cation retardation by a factor of more than 1000.

  9. HNS+ and HSN+ cations: Electronic states, spin-rovibronic spectroscopy with planetary and biological implications (United States)

    Trabelsi, Tarek; Ben Yaghlane, Saida; Al Mogren, Muneerah Mogren; Francisco, Joseph S.; Hochlaf, Majdi


    Ab initio methods in conjunction with a large basis set are used to compute the potential energy surfaces of the 12 lowest electronic states of the HNS+ and HSN+ isomeric forms. These potentials are used in discussions of the metastability of these cations and plausible mechanisms for the H+/H + SN+/SN, S/S+ + NH+/NH, N/N+ + SH+/SH ion-molecule reactions. Interestingly, the low rovibrational levels of HSN+(12A″) and HNS+(12A″) electronically excited ions are predicted to be long-lived. Both ions are suggested to be a suitable candidate for light-sensitive NOṡ donor in vivo and as a possible marker for the detection of intermediates in nitrites + H2S reactions at the cellular level. The full spin rovibronic levels of HNS+ are presented, which may assist in the experimental identification of HNS+ and HSN+ ions and in elucidating their roles in astrophysical and biological media.


    Institute of Scientific and Technical Information of China (English)



    A new algorithm for the stabilization of (possibly turbulent, chaotic) distributed systems, governed by linear or non linear systems of equations is presented. The SPA (Stabilization Parallel Algorithm) is based on a systematic parallel decomposition of the problem (related to arbitrarily overlapping decomposition of domains) and on a penalty argument. SPA is presented here for the case of linear parabolic equations: with distrjbuted or boundary control. It extends to practically all linear and non linear evolution equations, as it will be presented in several other publications.

  11. Using Drosophila for Studies of Intermediate Filaments. (United States)

    Bohnekamp, Jens; Cryderman, Diane E; Thiemann, Dylan A; Magin, Thomas M; Wallrath, Lori L


    Drosophila melanogaster is a useful organism for determining protein function and modeling human disease. Drosophila offers a rapid generation time and an abundance of genomic resources and genetic tools. Conservation in protein structure, signaling pathways, and developmental processes make studies performed in Drosophila relevant to other species, including humans. Drosophila models have been generated for neurodegenerative diseases, muscular dystrophy, cancer, and many other disorders. Recently, intermediate filament protein diseases have been modeled in Drosophila. These models have revealed novel mechanisms of pathology, illuminated potential new routes of therapy, and make whole organism compound screens feasible. The goal of this chapter is to outline steps to study intermediate filament function and model intermediate filament-associated diseases in Drosophila. The steps are general and can be applied to study the function of almost any protein. The protocols outlined here are for both the novice and experienced Drosophila researcher, allowing the rich developmental and cell biology that Drosophila offers to be applied to studies of intermediate filaments.

  12. C and C* among intermediate rings

    NARCIS (Netherlands)

    J. Sack; S. Watson


    Given a completely regular Hausdorff space X, an intermediate ring A(X) is a ring of real valued continuous functions between C*(X) and C(X). We discuss two correspondences between ideals in A(X) and z-filters on X, both reviewing old results and introducing new results. One correspondence, ZA, exte

  13. What Should be Taught in Intermediate Macroeconomics? (United States)

    de Araujo, Pedro; O'Sullivan, Roisin; Simpson, Nicole B.


    A lack of consensus remains on what should form the theoretical core of the undergraduate intermediate macroeconomic course. In determining how to deal with the Keynesian/classical divide, instructors must decide whether to follow the modern approach of building macroeconomic relationships from micro foundations, or to use the traditional approach…

  14. Synthesis of the key intermediate of ramelteon

    Institute of Scientific and Technical Information of China (English)

    Shan Bao Yu; Hao Min Liu; Yu Luo; Wei Lu


    Asymmetric conjugated addition of allylcopper reagents derived from an allyl Grignard reagent and CuBr·Me2S to chiral α,β-unsaturated N-acyl oxazolidinones has been achieved. The synthetic procedure was applied to the preparation of the key intermediate of the novel nonbenzodiazepine hypnotic drug, ramelteon.

  15. Korean Intermediate Course. Selected Newspaper Articles. (United States)

    Defense Language Inst., Washington, DC.

    The purpose of this material is to provide reading matter for the last phase of the Defense Language Institute's extended and intermediate courses in Korean. (See ED 024 943 for the Korean Basic Course, Lesson Units 1-112.) The content of this volume is current, introduces important vocabulary not encountered elsewhere in the courses, and calls…

  16. C and C* among intermediate rings

    NARCIS (Netherlands)

    Sack, J.; Watson, S.


    Given a completely regular Hausdorff space X, an intermediate ring A(X) is a ring of real valued continuous functions between C*(X) and C(X). We discuss two correspondences between ideals in A(X) and z-filters on X, both reviewing old results and introducing new results. One correspondence, ZA, exte

  17. Teaching Vocabulary and Morphology in Intermediate Grades (United States)

    Palumbo, Anthony; Kramer-Vida, Louisa; Hunt, Carolyn V.


    Direct vocabulary instruction of Tier 2 and Tier 3 words in intermediate-grade curricula is an important tool of literacy instruction because English is a language grafted from many roots and has not developed a one-to-one phoneme-grapheme correspondence. In addition to knowing graphemes and phonemes, students must formally learn words that cross…

  18. Changes to the Intermediate Accounting Course Sequence (United States)

    Davidson, Lesley H.; Francisco, William H.


    There is an ever-growing amount of information that must be covered in Intermediate Accounting courses. Due to recent accounting standards and the implementation of IFRS this trend is likely to continue. This report incorporates the results of a recent survey to examine the trend of spending more course time to cover this additional material.…

  19. Essays in corporate finance and financial intermediation

    NARCIS (Netherlands)

    Kempf, Elisabeth


    This thesis consists of three chapters in corporate finance and financial intermediation. The first two chapters explore sources of incentives and learning for finance professionals. Specifically, the first chapter studies how the option to go work for an investment bank affects the incentives of cr

  20. Intermediates and Generic Convergence to Equilibria

    DEFF Research Database (Denmark)

    Freitas, Michael Marcondes de; Wiuf, Carsten; Feliu, Elisenda


    Known graphical conditions for the generic or global convergence to equilibria of the dynamical system arising from a reaction network are shown to be invariant under the so-called successive removal of intermediates, a systematic procedure to simplify the network, making the graphical conditions...

  1. Bismuth phosphates as intermediate temperature proton conductors

    DEFF Research Database (Denmark)

    Huang, Yunjie; Christensen, Erik; Shuai, Qin


    Proton conducting electrolyte materials operational in the intermediate temperature range of 200-400 °C are of special interest for applications in fuel cells and water electrolysers. Bismuth phosphates in forms of polycrystalline powders and amorphous glasses are synthesized and investigated...

  2. Bridge: Intelligent Tutoring with Intermediate Representations (United States)


    Research and Development Center and Psychology Department University of Pittsburgh Pittsburgh, PA. 15260 The Artificial Intelligence and Psychology...problem never introduces more than one unfamiliar plan. Inteligent Tutoring With Intermediate Representations - Bonar and Cunniigbam 4 You must have a... Inteligent Tutoring With ntermediate Representations - Bonar and Cunningham 7 The requirements are specified at four differcnt levels, corresponding to

  3. Software Testing An ISEB Intermediate Certificate

    CERN Document Server

    Hambling, Brian


    Covering testing fundamentals, reviews, testing and risk, test management and test analysis, this book helps newly qualified software testers to learn the skills and techniques to take them to the next level. Written by leading authors in the field, this is the only official textbook of the ISEB Intermediate Certificate in Software Testing.

  4. Modern Persian: Intermediate Level, Vol. 2. (United States)

    Windfuhr, Gernot; And Others

    The second of three volumes of an intergrated course in intermediate Persian is presented. This volume encompasses material appropriate for students entering the second year of Persian studies who have strong preparation in elementary Persian. Verbal skills should be on a level which will allow comprehensive discussion of a topic using simple,…

  5. The GEOTRACES Intermediate Data Product 2014

    NARCIS (Netherlands)

    Mawji, Edward; Schlitzer, Reiner; Dodas, Elena Masferrer; Abadie, Cyril; Abouchami, Wafa; Anderson, Robert F.; Baars, Oliver; Bakker, Karel; Baskaran, Mark; Bates, Nicholas R.; Bluhm, Katrin; Bowie, Andrew; Bown, Johann; Boye, Marie; Boyle, Edward A.; Branellec, Pierre; Bruland, Kenneth W.; Brzezinski, Mark A.; Bucciarelli, Eva; Buesseler, Ken; Butler, Edward; Cai, Pinghe; Cardinal, Damien; Casciotti, Karen; Chaves, Joaquin; Cheng, Hai; Chever, Fanny; Church, Thomas M.; Colman, Albert S.; Conway, Tim M.; Croot, Peter L.; Cutter, Gregory A.; de Souza, Gregory F.; Dehairs, Frank; Deng, Feifei; Huong Thi Dieu, [Unknown; Dulaquais, Gabriel; Echegoyen-Sanz, Yolanda; Edwards, R. Lawrence; Fahrbach, Eberhard; Fitzsimmons, Jessica; Fleisher, Martin; Frank, Martin; Friedrich, Jana; Fripiat, Francois; Galer, Stephen J. G.; Gamo, Toshitaka; Solsona, Ester Garcia; Gerringa, Loes J. A.; Godoy, Jose Marcus; Gonzalez, Santiago; Grossteffan, Emilie; Hatta, Mariko; Hayes, Christopher T.; Heller, Maija Iris; Henderson, Gideon; Huang, Kuo-Fang; Jeandel, Catherine; Jenkins, William J.; John, Seth; Kenna, Timothy C.; Klunder, Maarten; Kretschmer, Sven; Kumamoto, Yuichiro; Laan, Patrick; Labatut, Marie; Lacan, Francois; Lam, Phoebe J.; Lannuzel, Delphine; le Moigne, Frederique; Lechtenfeld, Oliver J.; Lohan, Maeve C.; Lu, Yanbin; Masque, Pere; McClain, Charles R.; Measures, Christopher; Middag, Rob; Moffett, James; Navidad, Alicia; Nishioka, Jun; Noble, Abigail; Obata, Hajime; Ohnemus, Daniel C.; Owens, Stephanie; Planchon, Frederic; Pradoux, Catherine; Puigcorbe, Viena; Quay, Paul; Radic, Amandine; Rehkaemper, Mark; Remenyi, Tomas; Rijkenberg, Micha J. A.; Rintoul, Stephen; Robinson, Laura F.; Roeske, Tobias; Rosenberg, Mark; van der Loeff, Michiel Rutgers; Ryabenko, Evgenia; Saito, Mak A.; Roshan, Saeed; Salt, Lesley; Sarthou, Geraldine; Schauer, Ursula; Scott, Peter; Sedwick, Peter N.; Sha, Lijuan; Shiller, Alan M.; Sigman, Daniel M.; Smethie, William; Smith, Geoffrey J.; Sohrin, Yoshiki; Speich, Sabrina; Stichel, Torben; Stutsman, Johnny; Swift, James H.; Tagliabue, Alessandro; Thomas, Alexander; Tsunogai, Urumu; Twining, Benjamin S.; van Aken, Hendrik M.; van Heuven, Steven; van Ooijen, Jan; van Weerlee, Evaline; Venchiarutti, Celia; Voelker, Antje H. L.; Wake, Bronwyn; Warner, Mark J.; Woodward, E. Malcolm S.; Wu, Jingfeng; Wyatt, Neil; Yoshikawa, Hisayuki; Zheng, Xin-Yuan; Xue, Zichen; Zieringer, Moritz; Zimmer, Louise A.; de Baar, Henricus


    The GEOTRACES Intermediate Data Product 2014 (IDP2014) is the first publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2013. It consists of two parts: (1) a compilation of digital data for more than 200 trace

  6. MNE Entrepreneurial Capabilities at Intermediate Levels

    DEFF Research Database (Denmark)

    Hoenen, Anne K.; Nell, Phillip Christopher; Ambos, Björn


    and on the heterogeneous information that is generated through dissimilar markets within the region. Our study opens up for an interesting discussion of the independence of these mechanisms. In sum, we contribute to the understanding of the entrepreneurial role of intermediate units in general and RHQs in particular....

  7. Intermediate Tamil: A Self-Instructional Method. (United States)

    Schiffman, Harold

    This self-instructional method for learning an intermediate level of Tamil is designed to follow an elementary level such as "Conversational Tamil." The material in this text concentrates on grammatical constructions not covered in that elementary text, particularly negatives of all kinds; in addition, this text uses the same transcription and the…

  8. On financial equilibrium with intermediation costs

    DEFF Research Database (Denmark)

    Markeprand, Tobias Ejnar


    This paper studies the set of competitive equilibria in financial economies with intermediation costs. We consider an arbitrary dividend structure, which includes options and equity with limited liabilities.We show a general existence result and upper-hemi continuity of the equilibrium correspond...

  9. Intermediality and politics in theatre and performance

    NARCIS (Netherlands)

    Dapp, G.S.


    This dissertation applies the concepts of intermediality and politics to five performances by Rimini Protokoll, Christoph Schlingensief, and Igneous, and analyzes the implications that emerge on both a significational and a theoretical level. Based on the specific mediality involved, it argues that

  10. Multiphase Gas in Intermediate Redshift Galaxies

    CERN Document Server

    Churchill, C W; Charlton, J; Januzzi, B; Churchill, Chris; Mellon, Rick; Charlton, Jane


    We present 40 quasar absorption line systems at intermediate redshifts (z~1), with focus on one of the most kinematically complex known, as examples of how the unique capabilities of space-based and ground-based facilities can be combined to glean much broader insights into astrophysical systems.

  11. Trusted intermediating agents in electronic trade networks

    NARCIS (Netherlands)

    Klos, T.B.; Alkemade, F.


    Electronic commerce and trading of information goods significantly impact the role of intermediaries: consumers can bypass intermediating agents by forming direct links to producers. One reason that traditional intermediaries can still make a profit, is that they have more knowledge of the market, s

  12. Intermediate Amharic Cultural Reader. Final Report. (United States)

    Leslau, Wolf

    This reader is intended to provide material for the intermediate-level student of Amharic, as well as to introduce the student to the cultural and social life of Ethiopia. The 39 texts were each prepared by a different student at Haile Selassie I University, thus providing the reader with a variety of language styles. The Amharic texts are…

  13. Interactions between cationic liposomes and drugs or biomolecules

    Directory of Open Access Journals (Sweden)



    Full Text Available Multiple uses for synthetic cationic liposomes composed of dioctadecyldimethylammonium bromide (DODAB bilayer vesicles are presented. Drugs or biomolecules can be solubilized or incorporated in the cationic bilayers. The cationic liposomes themselves can act as antimicrobial agents causing death of bacteria and fungi at concentrations that barely affect mammalian cells in culture. Silica particles or polystyrene microspheres can be functionalized by coverage with DODAB bilayers or phospholipid monolayers. Negatively charged antigenic proteins can be carried by the cationic liposomes which generate a remarkable immunoadjuvant action. Nucleotides or DNA can be physically adsorbed to the cationic liposomes to be transferred to mammalian cells for gene therapy. An overview of the interactions between DODAB vesicles and some biomolecules or drugs clearly points out their versatility for useful applications in a near future.

  14. Interactions between cationic liposomes and drugs or biomolecules. (United States)

    Carmona-Ribeiro, A M


    Multiple uses for synthetic cationic liposomes composed of dioctadecyldimethylammonium bromide (DODAB) bilayer vesicles are presented. Drugs or biomolecules can be solubilized or incorporated in the cationic bilayers. The cationic liposomes themselves can act as antimicrobial agents causing death of bacteria and fungi at concentrations that barely affect mammalian cells in culture. Silica particles or polystyrene microspheres can be functionalized by coverage with DODAB bilayers or phospholipid monolayers. Negatively charged antigenic proteins can be carried by the cationic liposomes which generate a remarkable immunoadjuvant action. Nucleotides or DNA can be physically adsorbed to the cationic liposomes to be transferred to mammalian cells for gene therapy. An overview of the interactions between DODAB vesicles and some biomolecules or drugs clearly points out their versatility for useful applications in a near future.

  15. Thermally induced conversion of Mg2+ cation exchanged LTA, FAU, GIS and SOD zeolites: syntheses and characterization of γ-cordierite, a new Mg2Al4Si5O18 polymorph

    Directory of Open Access Journals (Sweden)



    Full Text Available The thermal behaviours of fully Mg2+ cation exchanged LTA, FAU (X and Y species, GIS and SOD zeolites were investigated in the temperature range from ambient to 1400 °C. The initial zeolite frameworks collapsed into amorphous intermediate substances after air heating between 800–850 °C. Prolonged annealing of these products above 850 °C induced recrystallization into sapphirine-like phases (Mg–LTA and Mg–FAUx zeolites and μ-cordierite (Mg–FAUy and Mg–GIS zeolites phases. These phases were unstable during further temperature/time treatment and between 1000–1100 °C, they polymorphously transformed into γ-cordierite, a new Mg2Al4Si5O18 polymorph. γ-Cordierite was formed as a transformation product from the investigated zeolite precursors, except for the Mg–SOD zeolite. Structurally the γ-cordierite phase is a modulated, Mg-stuffed derivative of cristobalite with the approximate composition Mg2Al4Si5O18, which precedes the appearance of α-cordierite. The orthorhombic unit cell dimensions calculated from X-ray powder diffraction pattern are: a = 16.387(7 Å, b = 8.835(4 Å, c = 7.853(3 Å. γ-Cordierite has a narrow range of temperature stability (1100–1200 °C and during prolonged temperature/time treatment, it is polymorphously transformed to the α-cordierite phase.

  16. Anaerobic Toxicity of Cationic Silver Nanoparticles (United States)

    The microbial toxicity of silver nanoparticles (AgNPs) stabilized with different capping agents was compared to that of Ag+ under anaerobic conditions. Three AgNPs were investigated: (1) negatively charged citrate-coated AgNPs (citrate-AgNPs), (2) minimally charged p...

  17. Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition. (United States)

    Weidman, Mark C; Seitz, Michael; Stranks, Samuel D; Tisdale, William A


    Colloidal perovskite nanoplatelets are a promising class of semiconductor nanomaterials-exhibiting bright luminescence, tunable and spectrally narrow absorption and emission features, strongly confined excitonic states, and facile colloidal synthesis. Here, we demonstrate the high degree of spectral tunability achievable through variation of the cation, metal, and halide composition as well as nanoplatelet thickness. We synthesize nanoplatelets of the form L2[ABX3]n-1BX4, where L is an organic ligand (octylammonium, butylammonium), A is a monovalent metal or organic molecular cation (cesium, methylammonium, formamidinium), B is a divalent metal cation (lead, tin), X is a halide anion (chloride, bromide, iodide), and n-1 is the number of unit cells in thickness. We show that variation of n, B, and X leads to large changes in the absorption and emission energy, while variation of the A cation leads to only subtle changes but can significantly impact the nanoplatelet stability and photoluminescence quantum yield (with values over 20%). Furthermore, mixed halide nanoplatelets exhibit continuous spectral tunability over a 1.5 eV spectral range, from 2.2 to 3.7 eV. The nanoplatelets have relatively large lateral dimensions (100 nm to 1 μm), which promote self-assembly into stacked superlattice structures-the periodicity of which can be adjusted based on the nanoplatelet surface ligand length. These results demonstrate the versatility of colloidal perovskite nanoplatelets as a material platform, with tunability extending from the deep-UV, across the visible, into the near-IR. In particular, the tin-containing nanoplatelets represent a significant addition to the small but increasingly important family of lead- and cadmium-free colloidal semiconductors.

  18. VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes. (United States)

    Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M


    Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7 - 20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ~13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies, all species behave similarly, the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ~18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section, but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them, all are in good agreement with theoretical ones confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models.

  19. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    NARCIS (Netherlands)

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.


    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both simi

  20. Automated dual capillary electrophoresis system with hydrodynamic injection for the concurrent determination of cations and anions

    Energy Technology Data Exchange (ETDEWEB)

    Pham, Thi Thanh Thuy; Mai, Thanh Duc [University of Basel, Department of Chemistry, Spitalstrasse 51, Basel 4056 (Switzerland); Centre for Environmental Technology and Sustainable Development (CETASD), Hanoi University of Science, Nguyen Trai Street 334, Hanoi (Viet Nam); Nguyen, Thanh Dam [Centre for Environmental Technology and Sustainable Development (CETASD), Hanoi University of Science, Nguyen Trai Street 334, Hanoi (Viet Nam); Sáiz, Jorge [Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering – University of Alcalá, Ctra. Madrid-Barcelona km 33.6, Alcalá de Henares, Madrid 28871 (Spain); Pham, Hung Viet, E-mail: [Centre for Environmental Technology and Sustainable Development (CETASD), Hanoi University of Science, Nguyen Trai Street 334, Hanoi (Viet Nam); Hauser, Peter C., E-mail: [University of Basel, Department of Chemistry, Spitalstrasse 51, Basel 4056 (Switzerland)


    Highlights: • Concurrent determination of cations and anions was carried out by electrophoretic separation. • Optimized conditions for each class of analystes was possible by using separate capillaries. • Simultaneous hydrodynamic injection was carried out. • Pneumatic actuation was used for flushing and sample handling. • The denitrification of drinking water was successfully demonstrated. - Abstract: The capillary electrophoresis instrument developed for the concurrent determination of cations and anions features two separate capillaries and individual detectors to allow independent optimization for each group of ions. The capillaries are joined in a common injector block. The sample is drawn into the injector with a small membrane pump and automated simultaneous injection into both capillaries is achieved by pressurization of the fluid with compressed air. Flushing of the injector and of the capillaries with the background electrolyte is also carried out automatically by the same means. The buffer consisted of 12 mM histidine and 2 mM 18-crown-6 adjusted to pH 4 with acetic acid and was suitable for the contactless conductivity detection employed. The system was optimized for the determination of cationic NH{sub 4}{sup +} and anionic NO{sub 3}{sup −} and NO{sub 2}{sup −}, and linear calibration curves from about 20 μM up to about 1.5 mM were obtained for these ions. In a test run over 8 h, the reproducibility for the peak areas was within ±7%. For demonstration, the instrument was successfully applied to the concurrent monitoring of the concentrations of the three ions during the biological removal of ammonium from contaminated groundwater in a sequencing batch reactor, where NO{sub 3}{sup −} and NO{sub 2}{sup −} are formed as intermediate products.

  1. Macroeconomic stability

    DEFF Research Database (Denmark)

    Jespersen, Jesper


    It is demonstrated that full employment and sustainable development not necessarily are conflicting goals. On the other hand macroeconomic stability cannot be obtained without a deliberate labour sharing policy and a shift in the composition of private consumption away from traditional material...

  2. Insights in understanding aggregate formation and dissociation in cation exchange chromatography for a structurally unstable Fc-fusion protein. (United States)

    Chen, Zhiqiang; Huang, Chao; Chennamsetty, Naresh; Xu, Xuankuo; Li, Zheng Jian


    Cation-exchange chromatography (CEX) of a structurally unstable Fc-fusion protein exhibited multi-peak elution profile upon a salt-step elution due to protein aggregation during intra-column buffer transition where low pH and high salt coexisted. The protein exhibited a single-peak elution behavior during a pH-step elution; nevertheless, the levels of soluble aggregates (i.e. high molecular weight species, HMW) in the CEX eluate were still found up to 12-fold higher than that for the load material. The amount of the aggregates formed upon the pH-step elution was dependent on column loading with maximum HMW achieved at intermediate loading levels, supporting the hypothesis that the aggregation was the result of both the conformational changes of the bound protein and the solution concentration of the aggregation-susceptible proteins during elution. Factors such as high load pH, short protein/resin contact time, hydrophilic resin surface, and weak ionizable ligand were effective, to some extent, to reduce aggregate formation by improving the structural integrity of the bound protein. An orthogonal technique, differential scanning fluorimetry (DSF) using Sypro Orange dye confirmed that the bound protein exposed more hydrophobic area than the native molecule in free solution, especially in the pH 4-5 range. The Sypro Orange dye study of resin surface property also demonstrated that the poly[styrene-divinylbenzene]-based Poros XS with polyhydroxyl surface coating is more hydrophobic compared to the agarose-based CM Sepharose FF and SP Sepharose FF. The hydrophobic property of Poros XS contributed to stronger interactions with the partially unfolded bound protein and consequently to the higher aggregate levels seen in Poros XS eluate. This work also investigates the aggregation reversibility in CEX eluate where up to 66% of the aggregates were observed to dissociate into native monomers over a period of 120h, and links the aggregate stability to such conditions as resin

  3. Intermediate fragmentation per se provides stable predator-prey metapopulation dynamics. (United States)

    Cooper, Jennifer K; Li, Jiqiu; Montagnes, David J S


    The extent to which a landscape is fragmented affects persistence of predator-prey dynamics. Increasing fragmentation concomitantly imposes conditions that stabilise and destabilise metapopulations. For the first time, we explicitly assessed the hypothesis that intermediate levels provide optimal conditions for stability. We examine four structural changes arising from increased fragmentation: increased fragment number; decreased fragment size; increased connectedness (corridors scaled to fragment); increased fragment heterogeneity (based on connectedness). Using the model predator-prey system (Didinium-Paramecium) we support our hypothesis, by examining replicated metapopulations dynamics at five fragmentation levels. Although both species became extinct without fragmentation, prey survived at low and high levels, and both survived at intermediate levels. By examining time to extinction, maximum abundances, and population asynchrony we conclude that fragmentation produces structural heterogeneity (independent of environmental heterogeneity), which influences stability. Our analysis suggests why some theoretical, field and microcosm studies present conflicting views of fragmentation effects on population persistence.

  4. Degradation of cationic red GTL by catalytic wet air oxidation over Mo-Zn-Al-O catalyst under room temperature and atmospheric pressure. (United States)

    Xu, Yin; Li, Xiaoyi; Cheng, Xiang; Sun, Dezhi; Wang, Xueye


    To overcome the drawback of catalytic wet air oxidation (CWAO) with high temperature and high pressure, the catalytic activity of Mo-Zn-Al-O catalyst for degradation of cationic red GTL under room temperature and atmospheric pressure was investigated. Mo-Zn-Al-O catalyst was prepared by coprecipitation and impregnation. XRD, TG-DTG, and XPS were used to characterize the resulting sample. Central composition design using response surface methodology was employed to optimize correlation of factors on the decolorization of cationic red GTL. The results show that the optimal conditions of pH value, initial concentration of dye and catalyst dosage were found to be 4.0, 85 mg/L and 2.72 g/L, respectively, for maximum decolorization of 80.1% and TOC removal of 50.9%. Furthermore, the reaction on the Mo-Zn-Al-O catalyst and degradation mechanism of cationic red GTL was studied by Electron spin resonance (ESR) and GC-MS technique. The possible reaction mechanism was that the Mo-Zn-Al-O catalyst can efficiently react with adsorbed oxygen/H(2)O to produce ·OH and (1)O(2) and finally induce the degradation of cationic red GTL. GC-MS analysis of the degradation products indicates that cationic red GTL was initiated by the cleavage of -N ═ N- and the intermediates were further oxidized by ·OH or (1)O(2).

  5. Thermodynamics of cationic surfactant sorption onto natural clinoptilolite

    Energy Technology Data Exchange (ETDEWEB)

    Sullivan, E.J.; Bowman, R.S. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States); Carey, J.W. [Los Alamos National Lab., NM (United States)


    Sorption enthalpies of hexadecyltrimethylammonium bromide (HDTMA) as monomers and micelles and tetraethylammonium bromide (TEA) were used with surfactant, counterion, and co-ion sorption isotherms to infer the conformation, sorption mechanism, and relative stability of the sorbed surfactants on natural clinoptilolite. The average value of the sorption enthalpy was {minus}10.38 kJ/mol for monomers, {minus}11.98 kJ/mol for micelles, and +3.03 kJ/mol for TEA. Sorption of monomers produced a lower sorption plateau than equivalent micelle sorption (maxima 145 mmol/kg, 225 mmol/kg). Analysis of the sorption data demonstrated a change in the sorption mechanism at the external cation exchange capacity (ECEC) of clinoptilolite. Sorption data from below and above the ECEC were fit to a simple polynomial model and the Gibbs free energy of sorption ({Delta} G{sub m}{sup 0}) and sorption entropies were calculated. Resultant values of {Delta} G{sub m}{sup 0} were {minus}9.27 and {minus}14.38 kJ/mol for HDTMA monomers and micelles, respectively, for sorption below the ECEC, and {minus}16.11 and {minus}23.10 kJ/mol, respectively, for sorption above the ECEC. The value for TEA was {minus}1.04 kJ/mol, indicating weaker sorption than for HDTMA. Monomer sorption to clinoptilolite exceeded the ECEC, even when the solution concentration was below the critical micelle concentration. Hydrophobic (tail-tail) components of {Delta} G{sub m}{sup 0} were the driving force for sorption of HDTMA, both below and above the ECEC. A significant kinetic effect was observed in the sorption isotherms with a period of rapid sorption followed by slow equilibration requiring 7 days to achieve steady state for HDTMA; TEA equilibration occurred within 24 h.

  6. Riparian zone controls on base cation concentrations in boreal streams

    Directory of Open Access Journals (Sweden)

    J. L. J. Ledesma


    Full Text Available Forest riparian zones are a major in control of surface water quality. Base cation (BC concentrations, fluxes, and cycling in the riparian zone merit attention because of increasing concern of negative consequences for re-acidification of surface waters from future climate and forest harvesting scenarios. We present a two-year study of BC and silica (Si flow-weighted concentrations from 13 riparian zones and 14 streams in a boreal catchment in northern Sweden. The Riparian Flow-Concentration Integration Model (RIM was used to estimate riparian zone flow-weighted concentrations and tested to predict the stream flow-weighted concentrations. Spatial variation in BC and Si concentrations as well as in flow-weighted concentrations was related to differences in Quaternary deposits, with the largest contribution from lower lying silty sediments and the lowest contribution from wetland areas higher up in the catchment. Temporal stability in the concentrations of most elements, a remarkably stable Mg / Ca ratio in the soil water and a homogeneous mineralogy suggest that the stable patterns found in the riparian zones are a result of distinct mineralogical upslope groundwater signals integrating the chemical signals of biological and chemical weathering. Stream water Mg / Ca ratio indicates that the signal is subsequently maintained in the streams. RIM gave good predictions of Ca, Mg, and Na flow-weighted concentrations in headwater streams. The difficulty in modelling K and Si suggests a stronger biogeochemical influence on these elements. The observed chemical dilution effect with flow in the streams was related to variation in groundwater levels and element concentration profiles in the riparian zones. This study provides a first step toward specific investigations of the vulnerability of riparian zones to changes induced by forest management or climate change, with focus on BC or other compounds.

  7. Riparian zone control on base cation concentration in boreal streams

    Directory of Open Access Journals (Sweden)

    J. L. J. Ledesma


    Full Text Available Riparian zones (RZ are a major factor controlling water chemistry in forest streams. Base cations' (BC concentrations, fluxes, and cycling in the RZ merit attention because a changing climate and increased forest harvesting could have negative consequences, including re-acidification, for boreal surface waters. We present a two-year study of BC and silica (Si flow-weighted concentrations from 13 RZ and 14 streams in different landscape elements of a boreal catchment in northern Sweden. The spatial variation in BC and Si dynamics in both RZ and streams was explained by differences in landscape element type, with highest concentrations in silty sediments and lowest concentrations in peat-dominated wetland areas. Temporal stability in BC and Si concentrations in riparian soil water, remarkably stable Mg/Ca ratios, and homogeneous mineralogy suggest that patterns found in the RZ are a result of a distinct mineralogical upslope signal in groundwater. Stream water Mg/Ca ratios indicate that the signal is subsequently maintained in the streams. Flow-weighted concentrations of Ca, Mg, and Na in headwater streams were represented by the corresponding concentrations in the RZ, which were estimated using the Riparian Flow-Concentration Integration Model (RIM approach. Stream and RZ flow-weighted concentrations differed for K and Si, suggesting a stronger biogeochemical influence on these elements, including K recirculation by vegetation and retention of Si within the RZ. Potential increases in groundwater levels linked to forest harvesting or changes in precipitation regimes would tend to reduce BC concentrations from RZ to streams, potentially leading to episodic acidification.

  8. Cation Defects and Conductivity in Transparent Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Exarhos, Gregory J.; Windisch, Charles F.; Ferris, Kim F.; Owings, Robert R.


    High quality doped zinc oxide and mixed transition metal spinel oxide films have been deposited by means of sputter deposition from metal and metal oxide targets, and by spin casting from aqueous or alcoholic precursor solutions. Deposition conditions and post-deposition processing are found to alter cation oxidation states and their distributions in both oxide materials resulting in marked changes to both optical transmission and electrical response. For ZnO, partial reduction of the neat or doped material by hydrogen treatment of the heated film or by electrochemical processing renders the oxide n-type conducting. Continued reduction was found to diminish conductivity. In contrast, oxidation of the infrared transparent p-type spinel conductors typified by NiCo2O4 was found to increase conductivity. The disparate behavior of these two materials is caused in part by the sign of the charge carrier and by the existence of two different charge transport mechanisms that are identified as free carrier conduction and polaron hopping. While much work has been reported concerning structure/property relationships in the free carrier conducting oxides, there is a significantly smaller body of information on transparent polaron conductors. In this paper, we identify key parameters that promote conductivity in mixed metal spinel oxides and compare their behavior with that of the free carrier TCO’s.


    Directory of Open Access Journals (Sweden)

    Elina Orblin


    Full Text Available Papermaking pulps are a mixture of fibres, fibre fragments, and small cells (parenchyma or ray cells, usually called pulp fines. The interactions between pulp fines and a cationic copolymer of acrylamide and acryloxyethyltrimethyl ammonium chloride were investigated based on solid-liquid isotherms prepared under different turbulence, and subsequent advanced surface characterization using X-ray photoelectron spectroscopy (XPS and time-of-flight secondary ion mass spectrometry (ToF-SIMS. The surface charge and surface area of pulp fine substrates were measured by methylene blue sorption-XPS analysis and nitrogen adsorption combined with mercury porosimetry, respectively. The driving force behind polyelectrolyte adsorption was the amount of the surface anionic charge, whereas surface area appeared to be of less importance. Based on a comparison of solid-liquid and XPS sorption isotherms, different polyelectrolyte conformations were suggested, depending on the types of fines: A flatter conformation and partial cell-wall penetration of polyelectrolytes on kraft fines from freshly prepared pulp, and a more free conformation with extended loops and tails on lignocellulosic fines from recycled pulp. Additionally, ToF-SIMS imaging proved that recycled pulp fines contained residual de-inking chemicals (primarily palmitic acid salts that possibly hinder the electrostatic interactions with polyelectrolytes.

  10. Cationic Noncovalent Interactions: Energetics and Periodic Trends. (United States)

    Rodgers, M T; Armentrout, P B


    In this review, noncovalent interactions of ions with neutral molecules are discussed. After defining the scope of the article, which excludes anionic and most protonated systems, methods associated with measuring thermodynamic information for such systems are briefly recounted. An extensive set of tables detailing available thermodynamic information for the noncovalent interactions of metal cations with a host of ligands is provided. Ligands include small molecules (H2, NH3, CO, CS, H2O, CH3CN, and others), organic ligands (O- and N-donors, crown ethers and related molecules, MALDI matrix molecules), π-ligands (alkenes, alkynes, benzene, and substituted benzenes), miscellaneous inorganic ligands, and biological systems (amino acids, peptides, sugars, nucleobases, nucleosides, and nucleotides). Hydration of metalated biological systems is also included along with selected proton-based systems: 18-crown-6 polyether with protonated peptides and base-pairing energies of nucleobases. In all cases, the literature thermochemistry is evaluated and, in many cases, reanchored or adjusted to 0 K bond dissociation energies. Trends in these values are discussed and related to a variety of simple molecular concepts.

  11. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    Directory of Open Access Journals (Sweden)

    Anne-Marie Ellegaard


    Full Text Available Non-small cell lung cancer (NSCLC is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any non-localized cancer, and ebastine use showed a similar tendency. The association between CAD antihistamine use and reduced mortality was stronger among patients with records of concurrent chemotherapy than among those without such records. In line with this, sub-micromolar concentrations of loratadine, astemizole and ebastine sensitized NSCLC cells to chemotherapy and reverted multidrug resistance in NSCLC, breast and prostate cancer cells. Thus, CAD antihistamines may improve the efficacy of cancer chemotherapy.

  12. Interconnects for intermediate temperature solid oxide fuel cells (United States)

    Huang, Wenhua

    Presently, one of the principal goals of solid oxide fuel cells (SOFCs) research is to reduce the stack operating temperature to between 600 and 800°C. However, one of the principal technological barriers is the non-availability of a suitable material satisfying all of the stability requirements for the interconnect. In this work two approaches for intermediate temperature SOFC interconnects have been explored. The first approach comprises an interconnect consisting of a bi-layer structure, a p-type oxide (La0.96Sr0.08MnO 2.001/LSM) layer exposed to a cathodic environment, and an n-type oxide (Y0.08Sr0.88Ti0.95Al0.05O 3-delta/YSTA) layer exposed to anodic conditions. Theoretical analysis based on the bi-layer structure has established design criteria to implement this approach. The analysis shows that the interfacial oxygen partial pressure, which determines the interconnect stability, is independent of the electronic conductivities of both layers but dependent on the oxygen ion layer interconnects, the oxygen ion conductivities of LSM and YSTA were measured as a function of temperature and oxygen partial pressure. Based on the measured data, it has been determined that if the thickness of YSTA layer is around 0.1cm, the thickness of LSM layer should be around 0.6 mum in order to maintain the stability of LSM. In a second approach, a less expensive stainless steel interconnect has been studied. However, one of the major concerns associated with the use of metallic interconnects is the development of a semi-conducting or insulating oxide scale and chromium volatility during extended exposure to the SOFC operating environment. Dense and well adhered Mn-Cu spinet oxide coatings were successfully deposited on stainless steel by an electrophoretic deposition (EPD) technique. It was found that the Mn-Cu-O coating significantly reduced the oxidation rate of the stainless steel and the volatility of chromium. The area specific resistance (ASR) of coated Crofer 22 APU is

  13. Atmospheric fates of Criegee intermediates in the ozonolysis of isoprene. (United States)

    Nguyen, Tran B; Tyndall, Geoffrey S; Crounse, John D; Teng, Alexander P; Bates, Kelvin H; Schwantes, Rebecca H; Coggon, Matthew M; Zhang, Li; Feiner, Philip; Milller, David O; Skog, Kate M; Rivera-Rios, Jean C; Dorris, Matthew; Olson, Kevin F; Koss, Abigail; Wild, Robert J; Brown, Steven S; Goldstein, Allen H; de Gouw, Joost A; Brune, William H; Keutsch, Frank N; Seinfeld, John H; Wennberg, Paul O


    We use a large laboratory, modeling, and field dataset to investigate the isoprene + O3 reaction, with the goal of better understanding the fates of the C1 and C4 Criegee intermediates in the atmosphere. Although ozonolysis can produce several distinct Criegee intermediates, the C1 stabilized Criegee (CH2OO, 61 ± 9%) is the only one observed to react bimolecularly. We suggest that the C4 Criegees have a low stabilization fraction and propose pathways for their decomposition. Both prompt and non-prompt reactions are important in the production of OH (28% ± 5%) and formaldehyde (81% ± 16%). The yields of unimolecular products (OH, formaldehyde, methacrolein (42 ± 6%) and methyl vinyl ketone (18 ± 6%)) are fairly insensitive to water, i.e., changes in yields in response to water vapor (≤4% absolute) are within the error of the analysis. We propose a comprehensive reaction mechanism that can be incorporated into atmospheric models, which reproduces laboratory data over a wide range of relative humidities. The mechanism proposes that CH2OO + H2O (k(H2O)∼ 1 × 10(-15) cm(3) molec(-1) s(-1)) yields 73% hydroxymethyl hydroperoxide (HMHP), 6% formaldehyde + H2O2, and 21% formic acid + H2O; and CH2OO + (H2O)2 (k(H2O)2∼ 1 × 10(-12) cm(3) molec(-1) s(-1)) yields 40% HMHP, 6% formaldehyde + H2O2, and 54% formic acid + H2O. Competitive rate determinations (kSO2/k(H2O)n=1,2∼ 2.2 (±0.3) × 10(4)) and field observations suggest that water vapor is a sink for greater than 98% of CH2OO in a Southeastern US forest, even during pollution episodes ([SO2] ∼ 10 ppb). The importance of the CH2OO + (H2O)n reaction is demonstrated by high HMHP mixing ratios observed over the forest canopy. We find that CH2OO does not substantially affect the lifetime of SO2 or HCOOH in the Southeast US, e.g., CH2OO + SO2 reaction is a minor contribution (production by stabilized Criegees is likely unimportant in regions dominated by the reactivity of ozone with isoprene. In contrast

  14. Cation exchange resin nanocomposites based on multi-walled carbon nanotubes (United States)

    Fathy, Mahmoud; Abdel Moghny, Th.; Awad Allah, Ahmed Elsayed; Alblehy, AbdElhamid


    Carbon nanotubes (CNTs) are of great interest due to their potential applications in different fields such as water treatment and desalination. The increasing exploitation of multi-walled carbon nanotubes (MWCNTs) into many industrial processes has raised considerable concerns for environmental applications. The interactions of soluble salt with MWNCTs influence in the total salt content in saline water. In this work, we synthesized two cation exchange resins nano composites from polystyrene divinylbenzene copolymer (PSDVB) and pristine MWNCTs. The prepared compounds were characterized using infra red spectroscopy, thermal stability, X-ray diffraction, and electro scan microscope. Also, the ion capacities of prepared cation exchange resins were determined by titration. Based on the experimental results, it was found that the thermal stability of prepared nanocomposites in the presence of MWNCTs increased up to 617 °C. The X-ray of PSDVB and its sulfonated form exhibits amorphous pattern texture structure, whereas the nano composite exhibits amorphous structure with indication peak at 20° and 26° for the PSDVB and MWCNTs, respectively. The ion-exchange capacity increased from 225.6 meq/100 g to 466 mg/100 g for sulfonated PSDVB and sulfonated PSDVB MWNCTs-pristine, respectively.

  15. Cure Behaviors of epoxy resin initiated by methylanilinium slats as latent cationic curing agent.

    Energy Technology Data Exchange (ETDEWEB)

    Park, S.J.; Kim, T.J.; Lee, C.J.; Lee, J.R. [Korea Research Institute of Chemical Technology, Taejeon (Korea); Park, J.K.; Shin, J.H. [Seoul National University, Seoul (Korea)


    The effect of novel N-crotyl-N, N-dimethyl-4-methylanilinium hexafluoroantimonate (CMH) curing agent as a thermal latent initiator on thermal behaviors, rheological properties, and thermal stability of diglycidylether of bisphenol A (DGEBA) epoxy cationic system was investigated. From DSC measurements of DGEBA/CMH system, it was shown that this system exhibits an excellent thermal latent characteristic at a given temperature. The conversion and conversion rate of DGEBA/CMH system increased with increasing the concentration of initiator, due to high activity of CMH. Rheological properties of the system were investigated under isothermal condition using a rheometer. The gelation time was obtained from the analysis of storage modulus (G'), loss modulus (G''), and damping factor (tan {delta}). As a result, the reduction of gelation time was affected by high curing temperature and concentration of CMH, resulting in high degree of network formation in cationic polymerization, due to difference of activity. The thermal stability of the cured epoxy resin was discussed in terms of the activation energy for decomposition and thermal factors determined from TGA measurements. (author). 29 refs., 3 tabs., 10 figs.

  16. Lipopolysaccharide Neutralization by Cationic-Amphiphilic Polymers through Pseudoaggregate Formation. (United States)

    Uppu, Divakara S S M; Haldar, Jayanta


    Synthetic polymers incorporating the cationic charge and hydrophobicity to mimic the function of antimicrobial peptides (AMPs) have been developed. These cationic-amphiphilic polymers bind to bacterial membranes that generally contain negatively charged phospholipids and cause membrane disintegration resulting in cell death; however, cationic-amphiphilic antibacterial polymers with endotoxin neutralization properties, to the best of our knowledge, have not been reported. Bacterial endotoxins such as lipopolysaccharide (LPS) cause sepsis that is responsible for a great amount of mortality worldwide. These cationic-amphiphilic polymers can also bind to negatively charged and hydrophobic LPS and cause detoxification. Hence, we envisaged that cationic-amphiphilic polymers can have both antibacterial as well as LPS binding properties. Here we report synthetic amphiphilic polymers with both antibacterial as well as endotoxin neutralizing properties. Levels of proinflammatory cytokines in human monocytes caused by LPS stimulation were inhibited by >80% when coincubated with these polymers. These reductions were found to be dependent on concentration and, more importantly, on the side-chain chemical structure due to variations in the hydrophobicity profiles of these polymers. These cationic-amphiphilic polymers bind and cause LPS neutralization and detoxification. Investigations of polymer interaction with LPS using fluorescence spectroscopy and dynamic light scattering (DLS) showed that these polymers bind but neither dissociate nor promote LPS aggregation. We show that polymer binding to LPS leads to sort of a pseudoaggregate formation resulting in LPS neutralization/detoxification. These findings provide an unusual mechanism of LPS neutralization using novel synthetic cationic-amphiphilic polymers.

  17. Neutron diffraction investigations of kesterites: cation order and disorder

    Energy Technology Data Exchange (ETDEWEB)

    Schorr, Susan [Free University Berlin, Institute of Geological Sciences (Germany); Tovar, Michael [Helmholtz Zentrum Berlin fuer Materialien und Energie (Germany); Levcenco, Sergej; Napetrov, Alexander; Arushanov, Ernest [Academy of Sciences of Moldova Republic, Institute of Applied Physics, Chisinau (Moldova)


    The quaternary chalcogenides Cu{sub 2}ZnSnS{sub 4} and Cu{sub 2}ZnSnSe{sub 4} have newly attracted attention as possible absorber materials in thin film solar cells. They crystallize in the kesterite type (space group I anti 4) or stannite type structure (space group I anti 42m), which are described as an ordered distribution of the cations on different structural sites. Cation disorder may cause site defects and hence influences the electronic properties of the material. Thus the degree of cation order/disorder plays a crucial role and was therefor in the focus of the presented investigations. A differentiation between the isoelectronic cations Cu{sup +} and Zn{sup 2+} is not possible using X-ray diffraction due to their similar scattering power. But their neutron scattering lengths are different, thus neutron diffraction opens the possibility to determine the cation distribution in these compounds. A simultaneous Rietveld analysis of neutron and X-ray powder diffraction data revealed that in dependence on the thermal history of the samples cation disorder appears. The correlation trend between cation order/disorder and the sample growth method (solid state synthesis, Bridgman method) are discussed.

  18. Competitive Effects of 2+ and 3+ Cations on DNA Compaction

    CERN Document Server

    Tongu, C; Yoshikawa, Y; Zinchenko, A A; Chen, N; Yoshikawa, K


    By using single-DNA observation with fluorescence microscopy, we observed the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA with 166 kbp). It was found that divalent cations, such as Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. These experimental observations are inconsistent with the well-established Debye-Huckel scheme regarding the shielding effect of counter ions, which is given as the additivity of contributions of cations with different valences. We interpreted the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counter ions before and after the folding transition of DNA. For the compaction with SPD(3+), we considered the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly-charged polyelectrolyte, double-st...

  19. Atmospheric CO2 enrichment facilitates cation release from soil. (United States)

    Cheng, L; Zhu, J; Chen, G; Zheng, X; Oh, N-H; Rufty, T W; Richter, D deB; Hu, S


    Atmospheric CO(2) enrichment generally stimulates plant photosynthesis and nutrient uptake, modifying the local and global cycling of bioactive elements. Although nutrient cations affect the long-term productivity and carbon balance of terrestrial ecosystems, little is known about the effect of CO(2) enrichment on cation availability in soil. In this study, we present evidence for a novel mechanism of CO(2)-enhancement of cation release from soil in rice agricultural systems. Elevated CO(2) increased organic C allocation belowground and net H(+) excretion from roots, and stimulated root and microbial respiration, reducing soil redox potential and increasing Fe(2+) and Mn(2+) in soil solutions. Increased H(+), Fe(2+), and Mn(2+) promoted Ca(2+) and Mg(2+) release from soil cation exchange sites. These results indicate that over the short term, elevated CO(2) may stimulate cation release from soil and enhance plant growth. Over the long-term, however, CO(2)-induced cation release may facilitate cation losses and soil acidification, negatively feeding back to the productivity of terrestrial ecosystems.

  20. Cations bind only weakly to amides in aqueous solutions. (United States)

    Okur, Halil I; Kherb, Jaibir; Cremer, Paul S


    We investigated salt interactions with butyramide as a simple mimic of cation interactions with protein backbones. The experiments were performed in aqueous metal chloride solutions using two spectroscopic techniques. In the first, which provided information about contact pair formation, the response of the amide I band to the nature and concentration of salt was monitored in bulk aqueous solutions via attenuated total reflection Fourier transform infrared spectroscopy. It was found that molar concentrations of well-hydrated metal cations (Ca(2+), Mg(2+), Li(+)) led to the rise of a peak assigned to metal cation-bound amides (1645 cm(-1)) and a decrease in the peak associated with purely water-bound amides (1620 cm(-1)). In a complementary set of experiments, the effect of cation identity and concentration was investigated at the air/butyramide/water interface via vibrational sum frequency spectroscopy. In these studies, metal ion-amide binding led to the ordering of the adjacent water layer. Such experiments were sensitive to the interfacial partitioning of cations in either a contact pair with the amide or as a solvent separated pair. In both experiments, the ordering of the interactions of the cations was: Ca(2+) > Mg(2+) > Li(+) > Na(+) ≈ K(+). This is a direct cationic Hofmeister series. Even for Ca(2+), however, the apparent equilibrium dissociation constant of the cation with the amide carbonyl oxygen was no tighter than ∼8.5 M. For Na(+) and K(+), no evidence was found for any binding. As such, the interactions of metal cations with amides are far weaker than the analogous binding of weakly hydrated anions.

  1. Evolutionary Characteristics of China's Intermediate Manufactures

    Institute of Scientific and Technical Information of China (English)

    Minsung Kang; Jeong-Dong Lee


    China's economic development is characterized by progressive integration with international production chains as an assembly producer. Japan and South Korea are the major partners providing intermediate products to China. The present paper analyzes the Chinese intermediate sector's present condition and evolutionary characteristics revealed in bilateral trade with Japan and South Korea. The analysis uses the framework of new trade theory represented by "intra-industry trade". Trade statistics from 1997 to 2004 are analyzed using the database published by the OECD. Results show that China's inter-industrial evolution is characterized by its expanding positioning in the manner of the flying geese development paradigm of Asian countries. Furthermore, intra-industrial evolution is characterized by a concentration on price competitiveness. The framework and results of the industrial analysis presented in this paper assist in the understanding of China's manufacturing evolution and of the policy-making decisions taken in the process.

  2. Is TW Pictoris really an intermediate polar?

    CERN Document Server

    Norton, A J


    We present the results of a long ROSAT HRI observation of the candidate intermediate polar TW Pic. The power spectrum shows no sign of either the previously proposed white dwarf spin period or the proposed binary orbital period (1.996 hr and 6.06 hr respectively). The limits to the X-ray modulation are less than 0.3% in each case. In the absence of a coherent X-ray pulsation, the credentials of TW Pic for membership of the intermediate polar subclass must be suspect. We further suggest that the true orbital period of the binary may be the shorter of the two previously suggested, and that the longer period may represent a quasi-periodic phenomenon associated with the accretion disc.

  3. Being back home after intermediate care

    DEFF Research Database (Denmark)

    Martinsen, Bente; Harder, Ingegerd; Norlyk, Annelise


    Older people may face many challenges and experience insecurity after discharge from hospital to home. To bridge the potential gap between general hospital and home, the concept ‘Intermediate Care’ (IC) was developed at the beginning of 2000. IC aims to safeguard older people from being discharged....... Transcripts were analysed using a phenomenological approach. The essential meaning of being back home after a stay in an IC unit was characterised by ‘uncertainty’. Four constituents emerged: ‘in a state of shock about coming home’, ‘dependence on informal helpers’, ‘a sense of isolation’, and ‘fear of losing...... functional ability permanently’. Key words: intermediate care, older people, discharge, interview, phenomenology...

  4. A Mechanistic and Kinetic Study of the Photoinitiated Cationic Double Ring-opening Polymerization of 2-Methylene-7-phenyl-1,4,6,9-tetraoxa-spiro[4.4]nonane



    Efficient photopolymerization of a potentially expandable monomer is of practical importance for a variety of polymeric applications demanding dimensional stability, particularly if the polymerization process is well controlled based on a detailed investigation of the reaction. In the current study, photoinitiated polymerization kinetics of 2-methylene-7-phenyl-1,4,6,9-tetraoxaspiro[4.4]nonane (MPN) either with cationic initiation alone or with combined cationic/free radical initiation was ex...

  5. Aromatic C-H Bond Functionalization Induced by Electrochemically in Situ Generated Tris(p-bromophenyl)aminium Radical Cation: Cationic Chain Reactions of Electron-Rich Aromatics with Enamides. (United States)

    Li, Long-Ji; Jiang, Yang-Ye; Lam, Chiu Marco; Zeng, Cheng-Chu; Hu, Li-Ming; Little, R Daniel


    An effective Friedel-Crafts alkylation reaction of electron-rich aromatics with N-vinylamides, induced by electrochemically in situ-generated TBPA radical cation, has been developed; the resulting adducts are produced in good to excellent yields. In the "ex-cell" type electrolysis, TBPA is transformed to its oxidized form in situ and subsequently employed as an electron transfer reagent to initiate a cationic chain reaction. An easily recoverable and reusable polymeric ionic liquid-carbon black (PIL-CB) composite was also utilized as a supporting electrolyte for the electrochemical generation of TBPA cation radical, without sacrificing efficiency or stability after four electrolyses. Cyclic voltammetry analysis and the results of control experiments demonstrate that the reaction of electron-rich aromatics and N-vinylamides occurs via a cationic chain reaction, which takes place though an oxidative activation of a C-H bond of electron-rich aromatics instead of oxidation of the N-vinylamide as previously assumed.

  6. Cationic starches on cellulose surfaces. A study of polyelectrolyte adsorption.


    Steeg, van der, P.A.H.


    Cationic starches are used on a large scale in paper industry as wet-end additives. They improve dry strength. retention of fines and fillers, and drainage. Closure of the white water systems in the paper mills hase increased the concentration of detrimental substances. This might be the reason for the poor retention of cationic starches observed in the last few years.The purpose of the research described in this thesis was to obtain a better understanding of the adsorption of cationic starch...

  7. Electrostatic charge confinement using bulky tetraoctylammonium cation and four anions (United States)

    Andreeva, Nadezhda A.; Chaban, Vitaly V.


    Thanks to large opposite electrostatic charges, cations and anions establish strong ionic bonds. However, applications of ionic systems - electrolytes, gas capture, solubilization, etc. - benefit from weaker non-covalent bonds. The common approaches are addition of cosolvents and delocalization of electron charge density via functionalization of ions. We report fine tuning of closest-approach distances, effective radii, and cation geometry by different anions using the semi-empirical molecular dynamics simulations. We found that long fatty acid chains employed in the tetraalkylammonium cation are largely inefficient and new substituents must be developed. The reported results foster progress of task-specific ionic liquids.

  8. Competitive Solvation of the Imidazolium Cation by Water and Methanol

    CERN Document Server

    Chaban, Vitaly


    Imidazolium-based ionic liquids are widely used in conjunction with molecular liquids for various applications. Solvation, miscibility and similar properties are of fundamental importance for successful implementation of theoretical schemes. This work reports competitive solvation of the 1,3-dimethylimidazolium cation by water and methanol. Employing molecular dynamics simulations powered by semiempirical Hamiltonian (electronic structure level of description), the local structure nearly imidazolium cation is described in terms of radial distribution functions. Although water and methanol are chemically similar, water appears systematically more successful in solvating the 1,3-dimethylimidazolium cation. This result fosters construction of future applications of the ternary ion-molecular systems.

  9. Pyridine radical cation and its fluorine substituted derivatives (United States)

    Bondybey, V.E.; English, J.H.; Shiley, R.H.


    The spectra and relaxation of the pyridine cation and of several of its fluorinated derivatives are studied in low temperature Ne matrices. The ions are generated by direct photoionization of the parent compounds. Of the compounds studied, laser induced → and → fluorescence is observed only for the 2, 6‐difluoropyridine cation. The analysis of the spectrum indicates that the ion is planar both in the and states. The large variety in the spectroscopic and relaxation behavior of fluoropyridine radical cations is explained in terms of their electronic structure and of the differential shifts of the individual electronic states caused by the fluorine substitution.

  10. Discovery of the intermediate W boson

    CERN Multimedia


    Press conference on 25 January 1983 when the announcement was made of the discovery of the intermediate W boson at CERN. From right to left: Carlo Rubbia, spokesman of the UA1 experiment; Simon van der Meer, responsible for developing the stochastic cooling technique; Herwig Schopper, Director- General of CERN; Erwin Gabathuler, Research Director at CERN, and Pierre Darriulat, spokesman of the UA2 experiment, whose results confirmed those from Carlo Rubbia's experiment.

  11. Essays in corporate finance and financial intermediation



    This thesis consists of three chapters in corporate finance and financial intermediation. The first two chapters explore sources of incentives and learning for finance professionals. Specifically, the first chapter studies how the option to go work for an investment bank affects the incentives of credit rating analysts, and shows that this "revolving door" strengthens analysts' incentives to issue accurate ratings. The second chapter analyzes the value of experience for mutual fund managers a...

  12. International express student's book : pre-intermediate

    CERN Document Server

    Taylor, Liz


    The New Edition of International Express Pre-Intermediate retains all the keys features of this popular and successel four-level course. It combines engaging, up-to-date topics with a time-efficient and student-centred approach to language work, and clearly focused activities that reflect learner's real communicative needs - the ideal course for professional adults who use English for work, travel, and socializing.

  13. A high performance layered transition metal oxide cathode material obtained by simultaneous aluminum and iron cationic substitution (United States)

    El Mofid, Wassima; Ivanov, Svetlozar; Konkin, Alexander; Bund, Andreas


    The method of self-combustion synthesis was applied to prepare double Al- and Fe-substituted LiNi0.6Mn0.2Co0.15Al0.025Fe0.025O2 (NMCAF) and non-substituted LiNi0.6Mn0.2Co0.2O2 (NMC-3:1:1) cathode materials for lithium ion batteries. The novel NMCAF structure obtained by simultaneous cationic substitution showed an improved capacity and high stability during electrochemical cycling. X-ray diffraction patterns proved that both materials have a layered α-NaFeO2 type structure with a good hexagonal ordering. It was found that NMCAF has increased a and c lattice parameters due to a structural expansion caused by Al and Fe ion substitution. Rietveld refinement analysis revealed a significant decrease of the cationic mixing after the metal substitution, suggesting a structural stabilization. Electron paramagnetic resonance (EPR) spectroscopy showed that Al and Fe substitution markedly influenced the EPR spectrum of NMC-(3:1:1). The EPR spectral lines of both materials are attributed to Mn4+ and Ni2+ present in the structure. The change in the Ni2+ line after the metal substitution suggests a redistribution of the Ni ions in the structure, which can be related to the diminished cation mixing in the NMCAF. The improved electrochemical behavior of NMCAF is closely connected to the stabilization of the layered structure and the reduction of the cation mixing after metal substitution.

  14. Capturing a flavivirus pre-fusion intermediate.

    Directory of Open Access Journals (Sweden)

    Bärbel Kaufmann


    Full Text Available During cell entry of flaviviruses, low endosomal pH triggers the rearrangement of the viral surface glycoproteins to a fusion-active state that allows the release of the infectious RNA into the cytoplasm. In this work, West Nile virus was complexed with Fab fragments of the neutralizing mAb E16 and was subsequently exposed to low pH, trapping the virions in a pre-fusion intermediate state. The structure of the complex was studied by cryo-electron microscopy and provides the first structural glimpse of a flavivirus fusion intermediate near physiological conditions. A radial expansion of the outer protein layer of the virion was observed compared to the structure at pH 8. The resulting approximately 60 A-wide shell of low density between lipid bilayer and outer protein layer is likely traversed by the stem region of the E glycoprotein. By using antibody fragments, we have captured a structural intermediate of a virus that likely occurs during cell entry. The trapping of structural transition states by antibody fragments will be applicable for other processes in the flavivirus life cycle and delineating other cellular events that involve conformational rearrangements.

  15. Element Yields of Intermediate-Mass Stars

    CERN Document Server

    Henry, R B C


    Intermediate mass stars occupy the mass range between 0.8-8 solar masses. In this review, evolutionary models of these stars from numerous sources are compared in terms of their input physics and predicted yields. In particular, the results of Renzini & Voli, van den Hoek & Groenewegen, and Marigo are discussed. Generally speaking, it is shown that yields of He-4, C-12, and N-14 decrease with increasing metallicity, reduced mass loss rate, and increased rotation rate. Integrated yields and recently published chemical evolution model studies are used to assess the relative importance of intermediate mass and massive stars in terms of their contributions to universal element buildup. Intermediate mass stars appear to play a major role in the chemical evolution of N-14, a modest role in the case of C-12, and a small role for He-4. Furthermore, the time delay in their release of nuclear products appears to play an important part in explaining the apparent bimodality in the distribution of damped Lyman alp...

  16. New insights into the intracellular distribution pattern of cationic amphiphilic drugs (United States)

    Vater, Magdalena; Möckl, Leonhard; Gormanns, Vanessa; Schultz Fademrecht, Carsten; Mallmann, Anna M.; Ziegart-Sadowska, Karolina; Zaba, Monika; Frevert, Marie L.; Bräuchle, Christoph; Holsboer, Florian; Rein, Theo; Schmidt, Ulrike; Kirmeier, Thomas


    Cationic amphiphilic drugs (CADs) comprise a wide variety of different substance classes such as antidepressants, antipsychotics, and antiarrhythmics. It is well recognized that CADs accumulate in certain intracellular compartments leading to specific morphological changes of cells. So far, no adequate technique exists allowing for ultrastructural analysis of CAD in intact cells. Azidobupramine, a recently described multifunctional antidepressant analogue, allows for the first time to perform high-resolution studies of CADs on distribution pattern and morphological changes in intact cells. We showed here that the intracellular distribution pattern of azidobupramine strongly depends on drug concentration and exposure time. The mitochondrial compartment (mDsRed) and the late endo-lysosomal compartment (CD63-GFP) were the preferred localization sites at low to intermediate concentrations (i.e. 1 μM, 5 μM). In contrast, the autophagosomal compartment (LC3-GFP) can only be reached at high concentrations (10 μM) and long exposure times (72 hrs). At the morphological level, LC3-clustering became only prominent at high concentrations (10 μM), while changes in CD63 pattern already occurred at intermediate concentrations (5 μM). To our knowledge, this is the first study that establishes a link between intracellular CAD distribution pattern and morphological changes. Therewith, our results allow for gaining deeper understanding of intracellular effects of CADs. PMID:28281674

  17. Role of cluster size and substrate in the gas phase CC bond coupling reactions of allyl halides mediated by Agn+ and Agn-1H+ cluster cations (United States)

    Wang, Farrah Qiuyun; Khairallah, George N.; O'Hair, Richard A. J.


    Previous studies have demonstrated that the silver hydride cluster cation Ag4H+ promotes CC bond coupling of allylbromide [G.N. Khairallah, R.A.J. O'Hair, Angewandte Chemie International Edition 44 (2005) 728]. Here the influence of both the nature and the size of the silver cluster cation and the substrate on CC bond coupling are examined. Thus each of the cations Ag2H+, Ag4H+, Ag3+, and Ag5+ were allowed to react with three different halides: allyl chloride, allyl bromide and allyl iodide. No CC bond coupling is observed in the reactions of the cluster cations with allyl chloride. There are four main reaction sequences that result in CC bond coupling for allyl bromide and allyl iodide mediated by Agn+ and Agn-1H+ clusters: (i) A sequence involving the reactions of silver cluster cations with two molecules of C3H5X: Agn+ --> Agn(C3H5X)+ --> AgnX2+. This only occurs in the cases of: n = 3 and X = I; n = 5 and X = Br. (ii) A sequence involving the reactions of silver cluster cations with two molecules of C3H5X via an organometallic intermediate: Agn+ --> Agn-1(C3H5)+ --> Agn-1X+. This only occurs in the cases of: n = 5 and X = Br and I. (iii) A sequence involving the reactions of silver hydride cluster cations with three molecules of C3H5X: Agn-1H+ --> Agn-1X+ --> Agn-1X(C3H5X)+ --> Ag(C3H5)2+ and Agn-1X3+. This only occurs in the cases of: n = 5 and X = Br and I. (iv) A sequence involving the reactions of silver hydride cluster cations with three molecules of C3H5X via an organometallic intermediate: Agn-1H+ --> Agn-1X+ --> Agn-3(C3H5)+ --> Ag(C3H5)2+ and Agn-3X+. This only occurs in the cases of: n = 5 and X = I.

  18. Three iodometalate organic-inorganic hybrid materials based on methylene blue cation: Syntheses, structures, properties and DFT calculations (United States)

    Chai, Wen-Xiang; Lin, Jian; Song, Li; Qin, Lai-Shun; Shi, Hong-Sheng; Guo, Jia-Yu; Shu, Kang-Ying


    The functional dye of methylene blue (MB) has been employed for seeking new organic-inorganic hybrid photochromic materials. Although the photochromism has not been observed yet, three iodometalate compounds, namely (MB) (PbI3) (DMF) (1), (MB)4(Cu2I4)2 (2), and (MB)3(Bi2I9) (DMF)2 (3), have been synthesized and characterized. The iodometalate anion features as a [PbI3]∞- chain in 1, a dinuclear unit of Cu2I42- in 2, and a dinuclear unit of Bi2I93- in 3. Due to the synergy of cations and anions, the MB+ cations present supramolecular column stacks in 1 and 3, but a novel supramolecular octamer structure in 2. Their thermogravimetric analyses reveal that the polymeric inorganic anion structure is helpful to increase the stability of cation whereas the discrete structure is adverse. For seeking some clues which is significant to searching new photochromic systems, the density functional theory (DFT) studies have been performed on 1, in which the electronic structure analyses suggests that the stacking mode of cations and anions could be also an important factor influencing the charge transfer between them. In addition, dielectric hysteresis loop testing has been performed on 1 due to its polar space group of Cc.

  19. Delivery of siRNA using ternary complexes containing branched cationic peptides: the role of peptide sequence, branching and targeting. (United States)

    Kudsiova, Laila; Welser, Katharina; Campbell, Frederick; Mohammadi, Atefeh; Dawson, Natalie; Cui, Lili; Hailes, Helen C; Lawrence, M Jayne; Tabor, Alethea B


    Ternary nanocomplexes, composed of bifunctional cationic peptides, lipids and siRNA, as delivery vehicles for siRNA have been investigated. The study is the first to determine the optimal sequence and architecture of the bifunctional cationic peptide used for siRNA packaging and delivery using lipopolyplexes. Specifically three series of cationic peptides of differing sequence, degrees of branching and cell-targeting sequences were co-formulated with siRNA and vesicles prepared from a 1 : 1 molar ratio of the cationic lipid DOTMA and the helper lipid, DOPE. The level of siRNA knockdown achieved in the human alveolar cell line, A549-luc cells, in both reduced serum and in serum supplemented media was evaluated, and the results correlated to the nanocomplex structure (established using a range of physico-chemical tools, namely small angle neutron scattering, transmission electron microscopy, dynamic light scattering and zeta potential measurement); the conformational properties of each component (circular dichroism); the degree of protection of the siRNA in the lipopolyplex (using gel shift assays) and to the cellular uptake, localisation and toxicity of the nanocomplexes (confocal microscopy). Although the size, charge, structure and stability of the various lipopolyplexes were broadly similar, it was clear that lipopolyplexes formulated from branched peptides containing His-Lys sequences perform best as siRNA delivery agents in serum, with protection of the siRNA in serum balanced against efficient release of the siRNA into the cytoplasm of the cell.

  20. The geometry and efficacy of cation-pi interactions in a diagonal position of a designed beta-hairpin. (United States)

    Tatko, Chad D; Waters, Marcey L


    Cation-pi interactions are common in proteins, but their contribution to the stability and specificity of protein structure has not been well established. In this study, we examined the impact of cation-pi interactions in a diagonal position of a beta-hairpin peptide through comparison of the interaction of Phe or Trp with Lys or Arg. The diagonal interactions ranged from -0.20 to -0.48 kcal/mole. Our experimental values for the diagonal cation-pi interactions are similar to those found in alpha-helical studies. Upfield shifting of the Lys and Arg side chains indicates that the geometries of cation-pi interactions adopted in the 12-residue beta-hairpin are comparable to those found in protein structures. The Lys was found to interact through the polarized Cepsilon, and the Arg is stacked against the aromatic ring of Phe or Trp. Folding of these peptides was found to be enthalpically favorable (DeltaH degrees equals approximately -3 kcal/mole) and entropically unfavorable (DeltaS degrees equals approximately -8 cal mole(-1) K(-1)).

  1. IRMPD action spectroscopy of alkali metal cation-cytosine complexes: effects of alkali metal cation size on gas phase conformation. (United States)

    Yang, Bo; Wu, R R; Polfer, N C; Berden, G; Oomens, J; Rodgers, M T


    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both similar and distinctive spectral features over the range of ~1000-1900 cm(-1). The IRMPD spectra of the Li(+)(cytosine), Na(+)(cytosine), and K(+)(cytosine) complexes are relatively simple but exhibit changes in the shape and shifts in the positions of several bands that correlate with the size of the alkali metal cation. The IRMPD spectra of the Rb(+)(cytosine) and Cs(+)(cytosine) complexes are much richer as distinctive new IR bands are observed, and the positions of several bands continue to shift in relation to the size of the metal cation. The measured IRMPD spectra are compared to linear IR spectra of stable low-energy tautomeric conformations calculated at the B3LYP/def2-TZVPPD level of theory to identify the conformations accessed in the experiments. These comparisons suggest that the evolution in the features in the IRMPD action spectra with the size of the metal cation, and the appearance of new bands for the larger metal cations, are the result of the variations in the intensities at which these complexes can be generated and the strength of the alkali metal cation-cytosine binding interaction, not the presence of multiple tautomeric conformations. Only a single tautomeric conformation is accessed for all five alkali metal cation-cytosine complexes, where the alkali metal cation binds to the O2 and N3 atoms of the canonical amino-oxo tautomer of cytosine, M(+)(C1).

  2. Electrochemical reduction of oxygen in aprotic ionic liquids containing metal cations: Na-O2 system case study. (United States)

    Azaceta, Eneko; Lutz, Lukas; Grimaud, Alexis; Vicent-Luna, Jose Manuel; Hamad, Said; Yate, Luis; Cabañero, Geman; Grande, Hans-Jurgen; Anta, Juan Antonio; Tarascon, Jean-Marie; Tena-Zaera, Ramon


    Metal-air batteries are intensively studied because of their high theoretical energy storage capability. However, the fundamental science at work dealing with electrodes, electrolytes and reaction products still need to be better understood. In this report, the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR14TFSI) is chosen to study the influence of a wide range of metal cations (Mn+) on the electrochemical behavior of oxygen.. We demonstrate the relevance of the Lewis hard-soft acid-base (HSAB) theory to predict satisfactorily the reduction potential of the oxygen reduction in electrolytes containing metal cations. Systems with soft and intermediate Mn+ acidity are shown to facilitate oxygen reduction and metal oxide formation, whereas oxygen reduction is hampered by hard acid cations such as sodium (or lithium). Furthermore, the Density Functional Theory calculations on the energy formation of the resulting metal oxides rationalizes the effect of the Mn* on the oxygen reduction. The case study of Na-O2 system is described in detail. We show that, among others, the Na+ electrolyte concentration controls the electrochemical pathway, (solution precipitation vs. surface deposition) by which discharge product growth. All in all, fundamental insights to design advanced electrolytes for metal-air batteries and Na-air ones in particular are provided.

  3. Isomerization of propargyl cation to cyclopropenyl cation: Mechanistic elucidations and effects of lone pair donors

    Indian Academy of Sciences (India)

    Zodinpuia Pachuau; Kiew S Kharnaior; R H Duncan Lyngdoh


    This ab initio study examines two pathways (one concerted and the other two-step) for isomerization of the linear propargyl cation to the aromatic cyclopropenyl cation, also probing the phenomenon of solvation of this reaction by simple lone pair donors (NH3, H2O, H2S and HF) which bind to the substrate at two sites. Fully optimized geometries at the B3LYP/6-31G(d) level were used, along with single point QCISD(T)/6-311+G(d,p) and accurate G3 level calculations upon the DFT optimized geometries. For the unsolvated reaction, the two-step second pathway is energetically favoured over the one-step first pathway. Lone pair donor affinity for the various C3H$^{+}_{3}$ species follows the uniform order NH3 > H2S>H2O>HF. The activation barriers for the solvated isomerizations decrease in the order HF>H2O>H2S>NH3 for both pathways. The number of lone pairs on the donor heteroatom as well as the heteroatom electronegativity are factors related to both these trends. Compared to the unsolvated cases, the solvated reactions have transition states which are usually ‘later’ in position along the reaction coordinate, validating the Hammond postulate.

  4. Intermediate order in tetrahedrally coordinated silicon: evidence for chainlike objects

    Energy Technology Data Exchange (ETDEWEB)

    Tsu, D.V.; Chao, B.S.; Jones, S.J. [Energy Conversion Devices, Rochester Hills, MI (United States)


    In this report, we describe the nature of intermediate order in silicon as determined by recent measurements on thin films using transmission electron microscopy (TEM) and Raman scattering. The TEM images show in addition to the expected continuous random network (CRN), the presence of highly ordered quasi-one-dimensional ''chain-like objects'' (CLOs) that are 1-2 nm wide and tens of nm long that meander and show some evidence of cross-linking with each other. The presence of these objects correlate to a Raman feature centered at 490 cm{sup -1} whose width is 35-40 cm{sup -1}, and is used to quantify the heterogeneity in terms of the CLO and CRN (=475 cm{sup -1} scattering) concentrations. The 490 and 35 cm{sup -1} values are consistent with bond angle deviations approaching 0{sup o}, and thus reinforces an association with the CLOs. We find that in reference quality a-Si:H (made using pure SiH{sub 4}), the CLO concentration is about 5 vol%, while in state-of-the-art material using high H{sub 2} levels of dilution during processing, it increases to about 15%. Increased stability of such material to light-soaking is thus not mediated by a direct volumetric replacement of poor with high-quality components. Rather, an important characteristic of intermediate order in silicon is the low-dimensional aspect of its order, which allows it to influence more total volume than which it is itself composed. Consistent with these and other recent findings, we propose a tensegrity model of amorphous silicon. (author)

  5. Silica surfaces lubrication by hydrated cations adsorption from electrolyte solutions. (United States)

    Donose, Bogdan C; Vakarelski, Ivan U; Higashitani, Ko


    Adsorption of hydrated cations on hydrophilic surfaces has been related to a variety of phenomena associated with the short-range interaction forces and mechanisms of the adhesive contact between the surfaces. Here we have investigated the effect of the adsorption of cations on the lateral interaction. Using lateral force microscopy (LFM), we have measured the friction force between a silica particle and silica wafer in pure water and in electrolyte solutions of LiCl, NaCl, and CsCl salts. A significant lubrication effect was demonstrated for solutions of high electrolyte concentrations. It was found that the adsorbed layers of smaller and more hydrated cations have a higher lubrication capacity than the layers of larger and less hydrated cations. Additionally, we have demonstrated a characteristic dependence of the friction force on the sliding velocity of surfaces. A mechanism for the observed phenomena based on the microstructures of the adsorbed layers is proposed.

  6. Condensation of nonstochiometric DNA/polycation complexes by divalent cations. (United States)

    Budker, Vladimir; Trubetskoy, Vladimir; Wolff, Jon A


    This study found that divalent cations induced the further condensation of partially condensed DNA within nonstochiometric polycation complexes. The addition of a few mmol of a divalent cation such as calcium reduced by half the inflection point at which DNA became fully condensed by poly-L-lysine (PLL) and a variety of other polycations. The effect on DNA condensation was initially observed using a new method, which is based on the concentration-dependent self-quenching of fluorescent moieties (e.g., rhodamine) covalently linked to the DNA backbone at relatively high densities. Additional analyses, which employed ultracentrifugation, dynamic light scattering, agarose gel electrophoresis, and atomic force microscopy, confirmed the effect of divalent cations. These results provide an additional accounting of the process by which divalent cations induce greater chromatin compaction that is based on the representation of chromatin fibers as a nonstoichiometric polyelectrolyte complex. They also offer a new approach to assemble nonviral vectors for gene therapy.

  7. Suppression of the two-dimensional electron gas in LaGaO 3 /SrTiO 3 by cation intermixing

    KAUST Repository

    Nazir, S.


    Cation intermixing at the n-type polar LaGaO 3 /SrTiO 3 (001) interface is investigated by first principles calculations. Ti"Ga, Sr"La, and SrTi"LaGa intermixing are studied in comparison to each other, with a focus on the interface stability. We demonstrate in which cases intermixing is energetically favorable as compared to a clean interface. A depopulation of the Ti 3d xy orbitals under cation intermixing is found, reflecting a complete suppression of the two-dimensional electron gas present at the clean interface.

  8. Migration of Cations and Anions in Amorphous Polymer Electrolytes

    Institute of Scientific and Technical Information of China (English)

    N.A.Stolwijk; S.H.Obeidi; M.Wiencierz


    1 Results Polymer electrolytes are used as ion conductors in batteries and fuel cells.Simple systems consist of a polymer matrix complexing an inorganic salt and are fully amorphous at the temperatures of interest.Both cations and anions are mobile and contribute to charge transport.Most studies on polymer electrolytes use the electrical conductivity to characterize the ion mobility.However,conductivity measurements cannot discriminate between cations and anions.This paper reports some recent results fr...


    Institute of Scientific and Technical Information of China (English)

    W. Liu; Y. Ni; H. Xiao


    Hydrophilic and cationic montmorillonite is desirable for pitch control in the pulp and paper industry. In this paper, polyaminoamide - epichlorohydrin (PAE)modified montmorillonite was prepared. The modified montmorillonite was characterized using X-ray diffraction, FTIR and thermal gravimetric analysis. The amount of PAE intercalated and cationic charge densities of the modified montmorillonite were determined. Finally, it was found that both the solution and melt-intercalated samples with different charge densities exhibited strong interactions with dispersed colloidal rosin acid.

  10. Competition by meperidine for the organic cation renal excretory system. (United States)

    Acara, M; Gessner, T; Trudnowski, R J


    Renal tubular excretory transport of meperidine was studied using the Sperber preparation in chickens. When urine samples from infused and uninfused kidneys were analyzed for meperidine by gas chromatography, meperidine was always present in greater amounts in the urine from the infused kidney, demonstrating active tubular excretion. Meperidine at an infusion rate of 1 mumole/min, also inhibited the excretion of the organic cations choline and acetylcholine, indicating occupation of the renal organic cation excretory system in the chicken.

  11. Focused fluorescent probe library for metal cations and biological anions. (United States)

    Rhee, Hyun-Woo; Lee, Sang Wook; Lee, Jun-Seok; Chang, Young-Tae; Hong, Jong-In


    A focused fluorescent probe library for metal cations was developed by combining metal chelators and picolinium/quinolinium moieties as combinatorial blocks connected through a styryl group. Furthermore, metal complexes derived from metal chelators having high binding affinities for metal cations were used to construct a focused probe library for phosphorylated biomolecules. More than 250 fluorescent probes were screened for identifying an ultraselective probe for dTTP.

  12. Propagating phase interface with intermediate interfacial phase: Phase field approach (United States)

    Momeni, Kasra; Levitas, Valery I.


    An advanced three-phase phase field approach (PFA) is suggested for a nonequilibrium phase interface that contains an intermediate phase, in particular, a solid-solid interface with a nanometer-sized intermediate melt (IM). A thermodynamic potential in the polar order parameters is developed that satisfies all thermodynamic equilibrium and stability conditions. The special form of the gradient energy allowed us to include the interaction of two solid-melt interfaces via an intermediate melt and obtain a well-posed problem and mesh-independent solutions. It is proved that for stationary 1D solutions to two Ginzburg-Landau equations for three phases, the local energy at each point is equal to the gradient energy. Simulations are performed for β ↔δ phase transformations (PTs) via IM in an HMX energetic material. The obtained energy IM width dependence is described by generalized force-balance models for short- and long-range interaction forces between interfaces but not far from the melting temperature. A force-balance model is developed that describes phase field results even 100 K below the melting temperature. The effects of the ratios of width and energies of solid-solid and solid-melt interfaces, temperature, and the parameter characterizing interaction of two solid-melt interfaces, on the structure, width, energy of the IM and interface velocity are determined by finite element method. Depending on parameters, the IM may appear by continuous or discontinuous barrierless disordering or via critical nucleus due to thermal fluctuations. The IM may appear during heating and persist during cooling at temperatures well below than it follows from sharp-interface approach. On the other hand, for some parameters when IM is expected, it does not form, producing an IM-free gap. The developed PFA represents a quite general three-phase model and can be extended to other physical phenomena, such as martensitic PTs, surface-induced premelting and PTs, premelting

  13. Computer simulation of alkali metal cation-montmorillonite hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Fang-Ru Chou [Columbia Univ., Palisades, NY (United States); Skipper, N.T. [Univ. College, London (United Kingdom); Sposito, G. [Lawrence Berkeley National Lab., CA (United States)


    Molecular structure in the interlayers of Li-, Na-, or K-Wyoming montmorillonite with one, two, or three adsorbed water layers was investigated for the first time by concurrent Monte Carlo and molecular dynamics (MD) simulation, based on the Matsouka-Clementi-Yoshimine, (MCY) model of water-water interactions. Calculated layer spacings, as well as interlayer-species self-diffusion coefficients, were in good agreement with available experimental data. Inner-sphere surface complexes of the cations with tetrahedral charge sites were observed for all hydrates, whereas outer-sphere surface complexes of the cations with octahedral charge sites, found also in the one-layer hydrate, tended to dissociate from the clay mineral basal planes into a diffuse layer in the two- and three-layer hydrates. Differences in the interlayer water structure among the hydrates mainly reflected cation solvation, although some water molecules were entrapped within cavities in the montmorillonite surface. All of the interlayer cation and water species exchanged on the time scale (0.2 ns) of the MD simulations. Comparisons with results obtained using, instead of the MCY model, the TIP4P model for water-water, cation-water, and cation-clay interactions indicated that layer spacings and interlayer species mobilities tend to be under-predicted by the TIP4P model.

  14. Photochemical generation, isomerization, and oxygenation of stilbene cation radicals

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, F.D.; Bedell, A.M.; Dykstra, R.E.; Elbert, J.E. (Northwestern Univ., Evanston, IL (USA)); Gould, I.R.; Farid, S. (Eastman Kodak Co., Rochester, NY (USA))


    The cation radicals of cis- and trans-stilbene and several of their ring-substituted derivatives have been generated in solution directly by means of pulsed-laser-induced electron transfer to singlet cyanoanthracenes or indirectly via electron transfer from biphenyl to the singlet cyanoanthracene followed by secondary electron transfer from the stilbenes to the biphenyl cation radical. Transient absorption spectra of the cis- and trans-stilbene cation radicals generated by secondary electron transfer are similar to those previously obtained in 77 K matrices. Quantum yields for radical ion-pair cage escape have been measured for direct electron transfer from the stilbenes to three neutral and one charged singlet acceptor. These values increase as the ion-pair energy increases due to decreased rate constants for radical ion-pair return electron transfer, in accord with the predictions of Marcus theory for highly exergonic electron transfer. Cage-escape efficiencies are larger for trans- vs cis-stilbene cation radicals, possibly due to the greater extent of charge delocalization in the planar trans vs nonpolar cis cation radicals. Cage-escape stilbene cation radicals can initiate a concentration-dependent one way cis- {yields} trans-stilbene isomerization reaction.

  15. Tunable states of interlayer cations in two-dimensional materials

    Energy Technology Data Exchange (ETDEWEB)

    Sato, K.; Numata, K. [Department of Environmental Sciences, Tokyo Gakugei University, Koganei, Tokyo 184-8501 (Japan); Dai, W. [Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071 (China); Hunger, M. [Institute of Chemical Technology, University of Stuttgart, 70550 Stuttgart (Germany)


    The local state of cations inside the Ångstrom-scale interlayer spaces is one of the controlling factors for designing sophisticated two-dimensional (2D) materials consisting of 2D nanosheets. In the present work, the molecular mechanism on how the interlayer cation states are induced by the local structures of the 2D nanosheets is highlighted. For this purpose, the local states of Na cations in inorganic 2D materials, in which the compositional fluctuations of a few percent are introduced in the tetrahedral and octahedral units of the 2D nanosheets, were systematically studied by means of {sup 23}Na magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and {sup 23}Na multiple-quantum MAS (MQMAS) NMR spectroscopy. In contrast with an uniform distribution of Na cations expected so far, various well-defined cation states sensitive to the local structures of the 2D nanosheets were identified. The tunability of the interlayer cation states along with the local structure of the 2D nanosheets, as the smallest structural unit of the 2D material, is discussed.

  16. Synthesis and characterisation of cationically modified phospholipid polymers. (United States)

    Lewis, Andrew L; Berwick, James; Davies, Martyn C; Roberts, Clive J; Wang, Jin-Hai; Small, Sharon; Dunn, Anthony; O'Byrne, Vincent; Redman, Richard P; Jones, Stephen A


    Phospholipid-like copolymers based on 2-(methacryloyloxyethyl) phosphorylcholine were synthesised using monomer-starved free radical polymerisation methods and incorporating cationic charge in the form of the choline methacrylate monomer in amounts varying from 0 to 30 wt%, together with a 5 wt% silyl cross-linking agent in order to render them water-insoluble once thermally cured. Characterisation using a variety of techniques including nuclear magnetic resonance spectroscopy, high-pressure liquid chromatography and gel permeation chromatography showed the cationic monomer did not interfere with the polymerisation and that the desired amount of charge had been incorporated. Gravimetric and differential scanning calorimetry methods were used to evaluate the water contents of polymer membranes cured at 70 degrees C, which was seen to increase with increasing cation content, producing materials with water contents ranging from 50% to 98%. Surface plasmon resonance indicated that the coatings swelled rapidly in water, the rate and extent of swelling increasing with increasing cation level. Dynamic contact angle showed that coatings of all the polymers possessed a hydrophobic surface when dry in air, characteristic of the alkyl chains expressed at the surface (>100 degrees advancing angle). Rearrangement of the hydrophilic groups to the surface occurred once wet, to produce highly wettable surfaces with a decrease in advancing angle with increasing cation content. Atomic force microscopy showed all polymer films to be smooth with no features in topographical or phase imaging. Mechanical properties of the dry films were also unaffected by the increase in cation content.

  17. Modulatory role of bivalent cations on reward system. (United States)

    Nechifor, M; Chelărescu, D


    Bivalent cations (Ca, Mg, Zn, Mn etc.) modulate activity of reward system (RS). At physiologic levels they may influence all components of RS. There are influenced behavioral reactions at physiological stimuli and all essential elements of drug dependence (compulsive intake of substance, craving, reinforcement, withdrawal syndrom, relapse and reinstatement of intake) The fact that some cations (e.g. calcium) enhance some of the aspects of drug dependence and others (e.g. magnesium, zinc) decrease intensity of this process show that ratio between intra- and extracellular in the brain of these cations is important for the function of RS. Among actions of different cations at the level of RS there are important differences. Their mecahanism of action are common in part and specific in other. It is important the fact that modulatory action appear at physiologic cation concentrations (that could be reached at therapeutic doses). Modulatory action is related to ratio between concetrations of different bivalent cations and is exerted both in normal or pathologic conditions.

  18. Intermediate temperature solid oxide fuel cells. (United States)

    Brett, Daniel J L; Atkinson, Alan; Brandon, Nigel P; Skinner, Stephen J


    High temperature solid oxide fuel cells (SOFCs), typified by developers such as Siemens Westinghouse and Rolls-Royce, operate in the temperature region of 850-1000 degrees C. For such systems, very high efficiencies can be achieved from integration with gas turbines for large-scale stationary applications. However, high temperature operation means that the components of the stack need to be predominantly ceramic and high temperature metal alloys are needed for many balance-of-plant components. For smaller scale applications, where integration with a heat engine is not appropriate, there is a trend to move to lower temperatures of operation, into the so-called intermediate temperature (IT) range of 500-750 degrees C. This expands the choice of materials and stack geometries that can be used, offering reduced system cost and, in principle, reducing the corrosion rate of stack and system components. This review introduces the IT-SOFC and explains the advantages of operation in this temperature regime. The main advances made in materials chemistry that have made IT operation possible are described and some of the engineering issues and the new opportunities that reduced temperature operation affords are discussed. This tutorial review examines the advances being made in materials and engineering that are allowing solid oxide fuel cells to operate at lower temperature. The challenges and advantages of operating in the so-called 'intermediate temperature' range of 500-750 degrees C are discussed and the opportunities for applications not traditionally associated with solid oxide fuel cells are highlighted. This article serves as an introduction for scientists and engineers interested in intermediate temperature solid oxide fuel cells and the challenges and opportunities of reduced temperature operation.

  19. Spectroscopic studies of neutral and chemically oxidized species of β-carotene, lycopene and norbixin in CH{sub 2}Cl{sub 2}: Fluorescence from intermediate compounds

    Energy Technology Data Exchange (ETDEWEB)

    Alwis, D.D.D.H [Department of Chemistry, The Open University of Sri Lanka, Nawala (Sri Lanka); Department of Chemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka); Chandrika, U.G. [Department of Biochemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka); Jayaweera, P.M., E-mail: [Department of Chemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka)


    Radical cations, dications and oxidized intermediate species of three carotenoids, namely, β-carotene, lycopene and norbixin, were generated in CH{sub 2}Cl{sub 2} solutions via chemical oxidation using anhydrous FeCl{sub 3}. UV–vis, fluorescence and fluorescence-excitation spectroscopic studies were performed to understand and compare the nature of intermediate species generated during the chemical oxidation process and subsequent degradation. The intense emission observed at 550 nm can be assigned to the S{sub 2}→S{sub 0} (1{sup 1}B{sub u}→1{sup 1}A{sub g}) transition of the carotenoid molecules. The 350 nm excitation during the oxidation process for β-carotene, lycopene and norbixin exhibit intense fluorescence peaks at 492 nm, 493 nm and 500 nm, respectively. These peaks are assigned to intermediate peroxy/epoxy compounds of the three molecules that are formed with molecular oxygen prior to the formation of oxidized short-chain stable compounds. - Highlights: • Fluorescence and UV–vis studies on β-carotene, lycopene and norbixin. • Oxidation, induced by FeCl{sub 3} in CH{sub 2}Cl{sub 2} shows blue shifted fluorescence peaks. • Fluorescence peaks were assigned to intermediate peroxy/epoxy forms of carotenoids. • The D0→D3 transition of radical cations are observed in the near IR region.

  20. The intermediate age open cluster NGC 2660

    CERN Document Server

    Sandrelli, S; Tosi, M P; Marconi, G


    We present CCD UBVI photometry of the intermediate old open cluster NGC2660, covering from the red giants region to about seven magnitudes below the main sequence turn-off. Using the synthetic Colour - Magnitude Diagram method, we estimate in a self-consistent way values for distance modulus ((m-M)0 ~= 12.2), reddening (E(B-V) ~= 0.40), metallicity ([Fe/H] about solar), and age (age ~ 1 Gyr). A 30% population of binary stars turns out to be probably present.

  1. Observational constraints on dual intermediate inflation

    CERN Document Server

    Barrow, John D; Magueijo, João


    We explore the observational implications of models of intermediate inflation driven by modified dispersion relations, specifically those representing the phenomenon of dimensional reduction in the ultraviolet limit. These models are distinct from the standard ones because they do not require violations of the strong energy condition, and this is reflected in their structure formation properties. We find that they can naturally accommodate deviations from exact scale-invariance. They also make clear predictions for the running of the spectral index and tensor modes, rendering the models straightforwardly falsifiable. We discuss the observational prospects for these models and the implications these may have for quantum gravity scenarios.

  2. Thermoelectric power generator with intermediate loop (United States)

    Bell, Lon E; Crane, Douglas Todd


    A thermoelectric power generator is disclosed for use to generate electrical power from heat, typically waste heat. An intermediate heat transfer loop forms a part of the system to permit added control and adjustability in the system. This allows the thermoelectric power generator to more effectively and efficiently generate power in the face of dynamically varying temperatures and heat flux conditions, such as where the heat source is the exhaust of an automobile, or any other heat source with dynamic temperature and heat flux conditions.

  3. Organophosphate poisoning: Diagnosis of intermediate syndrome

    Directory of Open Access Journals (Sweden)

    Poojara L


    Full Text Available Organophosphate compound (OPC poisoning with suicidal intent is common in Indian ICUs. The effect of OPCs is to produce a persistent depolarization of the neuromuscular junction leading to muscle weakness. After initial recovery from cholinergic crisis, some patients have resurgence of respiratory muscle paralysis requiring continued ventilatory support. This is termed intermediate syndrome (IMS. This could be due to a change in the type of neuromuscular block to a non depolarisation block characterized by a fade on tetanic stimulation. However peripheral nerve stimulation using train-of-four ratio (TOF and/tetanus have failed to consistently show such a change. We elected to study whether electro physiological monitoring using repetitive nerve stimulation might show a decremental response during IMS. Material & Methods: This was a prospective blinded study done from April 2002 to March 2003 in our ICU. 45 consecutive patients of OPC poisoning admitted during this period were included in this study. Repetitive nerve stimulation (RNS using a train of ten at 3Hz 10Hz and 30Hz (slow , intermediate and fast speeds respectively at the median nerve was done on all patients on day 1, 4, 7 and every 4th day thereafter until discharge. Patients were ventilated until ready to wean as per our usual protocol. The results of the RNS study were not revealed to the intensivist. Results: 9 out of 45 patients required ventilation for more than 6 days and showed overt signs of intermediate syndrome - proximal muscle weakness, twitching and respiratory weakness. Only 2 patients out of the 9 had a decremental response on RNS at 3Hz indicating a post-junctional dysfunction at the motor end-plate, Both patients had consumed a very large quantity of OPC and were deeply comatose for >4 days and required ventilation for >12 days. All other patients with IMS showed no changes on RNS. The exact type of poison consumed varied with each individual patient. Conclusion: RNS

  4. q-Gamow States for intermediate energies

    CERN Document Server

    Plastino, A; Zamora, D J


    In a recent paper [Nuc. Phys. A {\\bf 948}, (2016) 19] we have demonstrated the possible existence of Tsallis' q-Gamow states. Now, accelerators' experimental evidence for Tsallis' distributions has been ascertained only at very high energies. Here, instead, we develop a different set of q-Gamow states for which the associated q-Breit-Wigner distribution could easily be found at intermediate energies, for which accelerators are available at many locations. In this context, it should be strongly emphasized [Physica A {\\bf 388} (2009) 601] that, empirically, one never exactly and unambiguously "detects" pure Gaussians, but rather q-Gaussians. A prediction is made via Eq.(3.30)

  5. Intermediate Bandgap Solar Cells From Nanostructured Silicon

    Energy Technology Data Exchange (ETDEWEB)

    Black, Marcie [Bandgap Engineering, Lincoln, MA (United States)


    This project aimed to demonstrate increased electronic coupling in silicon nanostructures relative to bulk silicon for the purpose of making high efficiency intermediate bandgap solar cells using silicon. To this end, we formed nanowires with controlled crystallographic orientation, small diameter, <111> sidewall faceting, and passivated surfaces to modify the electronic band structure in silicon by breaking down the symmetry of the crystal lattice. We grew and tested these silicon nanowires with <110>-growth axes, which is an orientation that should produce the coupling enhancement.

  6. Opening the Black Box of Intermediation

    DEFF Research Database (Denmark)

    Nowinska, Agnieszka

    ) and at the interfirm level (between partners and within alliances and associations).The tentative results show that both of these levels are important in defining the intermediating firms' business models and in answering their environmental threats and in building up competitive advantage. The paper ends with a short...... dynamics. This paper draws on qualitative data originating with interviews with industry representatives and can also be regarded as a preliminary approach to a broader project. The analysis distinguishes between relational capital at the intrafirm level (the network among the company's employees...

  7. Does the cation really matter? The effect of modifying an ionic liquid cation on an SN2 process. (United States)

    Tanner, Eden E L; Yau, Hon Man; Hawker, Rebecca R; Croft, Anna K; Harper, Jason B


    The rate of reaction of a Menschutkin process in a range of ionic liquids with different cations was investigated, with temperature-dependent kinetic data giving access to activation parameters for the process in each solvent. These data, along with molecular dynamics simulations, demonstrate the importance of accessibility of the charged centre on the cation and that the key interactions are of a generalised electrostatic nature.

  8. Sorption of the organic cation metoprolol on silica gel from its aqueous solution considering the competition of inorganic cations. (United States)

    Kutzner, Susann; Schaffer, Mario; Börnick, Hilmar; Licha, Tobias; Worch, Eckhard


    Systematic batch experiments with the organic monovalent cation metoprolol as sorbate and the synthetic material silica gel as sorbent were conducted with the aim of characterizing the sorption of organic cations onto charged surfaces. Sorption isotherms for metoprolol (>99% protonated in the tested pH of around 6) in competition with mono- and divalent inorganic cations (Na(+), NH4(+), Ca(2+), and Mg(2+)) were determined in order to assess their influence on cation exchange processes and to identify the role of further sorptive interactions. The obtained sorption isotherms could be described well by an exponential function (Freundlich isotherm model) with consistent exponents (about 0.8). In general, a decreasing sorption of metoprolol with increasing concentrations in inorganic cations was observed. Competing ions of the same valence showed similar effects. A significant sorption affinity of metoprolol with ion type dependent Freundlich coefficients KF,0.77 between 234.42 and 426.58 (L/kg)(0.77) could still be observed even at very high concentrations of competing inorganic cations. Additional column experiments confirm this behavior, which suggests the existence of further relevant interactions beside cation exchange. In subsequent batch experiments, the influence of mixtures with more than one competing ion and the effect of a reduced negative surface charge at a pH below the point of zero charge (pHPZC ≈ 2.5) were also investigated. Finally, the study demonstrates that cation exchange is the most relevant but not the sole mechanism for the sorption of metoprolol on silica gel.

  9. Cation Uptake and Allocation by Red Pine Seedlings under Cation-Nutrient Stress in a Column Growth Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Zhenqing; Balogh-Brunstad, Zsuzsanna; Grant, Michael R.; Harsh, James B.; Gill, Richard; Thomashow, Linda; Dohnalkova, Alice; Stacks, Daryl; Letourneau, Melissa; Keller, Chester K.


    Background and Aims Plant nutrient uptake is affected by environmental stress, but how plants respond to cation-nutrient stress is poorly understood. We assessed the impact of varying degrees of cation-nutrient limitation on cation uptake in an experimental plant-mineral system. Methods Column experiments, with red pine (Pinus resinosa Ait.) seedlings growing in sand/mineral mixtures, were conducted for up to nine months under a range of Ca- and K-limited conditions. The Ca and K were supplied from both minerals and nutrient solutions with varying Ca and K concentrations. Results Cation nutrient stress had little impact on carbon allocation after nine months of plant growth and K was the limiting nutrient for biomass production. The Ca/Sr and K/Rb ratio results allowed independent estimation of dissolution incongruency and discrimination against Sr and Rb during cation uptake processes. The fraction of K in biomass from biotite increased with decreasing K supply from nutrient solutions. The mineral anorthite was consistently the major source of Ca, regardless of nutrient treatment. Conclusions Red pine seedlings exploited more mineral K in response to more severe K deficiency. This did not occur for Ca. Plant discrimination factors must be carefully considered to accurately identify nutrient sources using cation tracers.

  10. Stabilities and partitioning of arenonium ions in aqueous media. (United States)

    Lawlor, D A; More O'Ferrall, R A; Rao, S N


    The phenathrenonium ion is formed as a reactive intermediate in the solvolysis of 9-dichloroacetoxy-9,10-dihydrophenanthrene in aqueous acetonitrile and undergoes competing reactions with water acting as a base and nucleophile. Measurements of product ratios in the presence of azide ion as a trap and 'clock' yield rate constants kp = 3.7 x 10(10) and kH2O = 1.5 x 10(8) s(-1), respectively. Combining these with rate constants for the reverse reactions (protonation of phenanthrene and acid-catalyzed aromatization of its water adduct) gives equilibrium constants pKa = -20.9 and pK(R) = -11.6. For a series of arenonium and benzylic cations, correlation of log kp with pKa, taking account of the limit to kp set by the relaxation of water (10(11) s(-1)), leads to extrapolation of kp = 9.0 x 10(10) s(-1) and pKa = -24.5 for the benzenonium ion and kp = 6.5 x 10(10) s(-1) and pKa = -22.5 for the 1-naphthalenonium ion. Combining these pKa's with estimates of equilibrium constants pKH2O for the hydration of benzene and naphthalene, and the relationship pKR = pKa + pKH2O based on Hess's law, gives pKR = -2.3 and -8.0 respectively, and highlights the inherent stability of the benzenonium ion. A correlation exists between the partitioning ratio, kp/kH2O, for carbocations reacting in water and KH2O the equilibrium constant between the respective reaction products, i.e., log(kp/kH2O) = 0.46pKH2O - 3.7. It implies that kp exceeds kH2O only when KH2O > 10(8). This is consistent with the proton transfer (a) possessing a lower intrinsic reactivity than reaction of the carbocation with water as a nucleophile and (b) being rate-determining in the hydration of alkenes (and dehydration of alcohols) except when the double bond of the alkene is unusually stabilized, as in the case of aromatic molecules.

  11. Intermediate product selection and blending in the food processing industry

    DEFF Research Database (Denmark)

    Kilic, Onur A.; Akkerman, Renzo; van Donk, Dirk Pieter


    This study addresses a capacitated intermediate product selection and blending problem typical for two-stage production systems in the food processing industry. The problem involves the selection of a set of intermediates and end-product recipes characterising how those selected intermediates...

  12. 49 CFR 37.201 - Intermediate and rest stops. (United States)


    ... 49 Transportation 1 2010-10-01 2010-10-01 false Intermediate and rest stops. 37.201 Section 37.201... DISABILITIES (ADA) Over-the-Road Buses (OTRBs) § 37.201 Intermediate and rest stops. (a) Whenever an OTRB makes an intermediate or rest stop, a passenger with a disability, including an individual using...

  13. Lack of association between a cationic protein and a cationic fluorosurfactant. (United States)

    Macakova, Lubica; Nordstierna, Lars; Karlsson, Göran; Blomberg, Eva; Furó, István


    Surface tension, 19F and 1H NMR spectroscopy, and cryotransmission electron microscopy are used to characterize the state of association in aqueous solutions of a fluorosurfactant CF3(CF2)nSO2NH(CH2)3-4N(CH3)3+ I- (n = 8, 6) with and without lysozyme added. In the absence of lysozyme, we find monomers, small aggregates, and large vesicles to coexist, with the individual fluorosurfactant molecules exchanging slowly (>1 ms) among those states. When both lysozyme and fluorosurfactant are present in the solution, they have no measurable influence on the physical state of the other. In contrast, a hydrogenated cationic surfactant with the same headgroup, hexadecyltrimethylammonium bromide, is shown to associate to lysozyme.

  14. On the stability of cationic complexes of neon with helium--solving an experimental discrepancy. (United States)

    Bartl, Peter; Denifl, Stephan; Scheier, Paul; Echt, Olof


    Helium nanodroplets are doped with neon and ionized by electrons. The size-dependence of the ion abundance of HenNex(+), identified in high-resolution mass spectra, is deduced for complexes containing up to seven neon atoms and dozens of helium atoms. Particularly stable ions are inferred from anomalies in the abundance distributions. Two pronounced anomalies at n = 11 and 13 in the HenNe(+) series confirm drift-tube data reported by Kojima et al. [T. M. Kojima et al., Z. Phys. D, 1992, 22, 645]. The discrepancy with previously published spectra of neon-doped helium droplets, which did not reveal any abundance anomalies [T. Ruchti et al., J. Chem. Phys., 1998, 109, 10679-10687; C. A. Brindle et al., J. Chem. Phys., 2005, 123, 064312], is most likely due to limited mass resolution, which precluded unambiguous analysis of contributions from different ions with identical nominal mass. However, calculated dissociation energies of HenNe(+) reported so far do not correlate with the present data, possibly because of challenges in correctly treating the linear, asymmetric [He-Ne-He](+) ionic core in HenNe(+). Anomalies identified in the distributions of HenNex(+) for x > 1, including prominent ones at He12Ne2(+) and He14Ne2(+), may help to better understand solvation of Ne(+) and Nex(+) in helium.

  15. Long G2 accumulates recombination intermediates and disturbs chromosome segregation at dysfunction telomere in Schizosaccharomyces pombe

    Energy Technology Data Exchange (ETDEWEB)

    Habib, Ahmed G.K.; Masuda, Kenta; Yukawa, Masashi; Tsuchiya, Eiko [Department of Molecular Biotechnology, Graduate School of Advanced Sciences of Matter, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Ueno, Masaru, E-mail: [Department of Molecular Biotechnology, Graduate School of Advanced Sciences of Matter, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Research Center for the Mathematics on Chromatin Live Dynamics, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan)


    Protection of telomere (Pot1) is a single-stranded telomere binding protein which is essential for chromosome ends protection. Fission yeast Rqh1 is a member of RecQ helicases family which has essential roles in the maintenance of genomic stability and regulation of homologous recombination. Double mutant between fission yeast pot1Δ and rqh1 helicase dead (rqh1-hd) maintains telomere by homologous recombination. In pot1Δ rqh1-hd double mutant, recombination intermediates accumulate near telomere which disturb chromosome segregation and make cells sensitive to microtubule inhibitors thiabendazole (TBZ). Deletion of chk1{sup +} or mutation of its kinase domain shortens the G2 of pot1Δ rqh1-hd double mutant and suppresses both the accumulation of recombination intermediates and the TBZ sensitivity of that double mutant. In this study, we asked whether the long G2 is the reason for the TBZ sensitivity of pot1Δ rqh1-hd double mutant. We found that shortening the G2 of pot1Δ rqh1-hd double mutant by additional mutations of wee1 and mik1 or gain of function mutation of Cdc2 suppresses both the accumulation of recombination intermediates and the TBZ sensitivity of pot1Δ rqh1-hd double mutant. Our results suggest that long G2 of pot1Δ rqh1-hd double mutant may allow time for the accumulation of recombination intermediates which disturb chromosome segregation and make cells sensitive to TBZ. - Ηighlights: • We show link between long G2 and accumulation of toxic recombination intermediates. • Accumulation of recombination intermediates at telomere results in TBZ sensitivity. • Activation of DNA damage checkpoint worsens cells' viability in presence of TBZ.

  16. Transformation of Vesicles in Aqueous Two-Phase System of an Anionic Gemini Surfactant and a Cationic Conventional Surfactant Mixture

    Institute of Scientific and Technical Information of China (English)

    JIANG Rong; HUANG Yi-Xiong; ZHAO Jian-Xi; HUANG Chang-Cang


    Transformation of vesicles formed in DTAB/C11-p-PhCNa aqueous surfactant two-phase (ASTP) was observed by the transmission electron microscopy (TEM). The trans-conformation of the gemini surfactant in the aggregates was considered to be the important factor for constructing the multi-lamellar structure of the vesicle wall. The cation-π interaction between the quaternary ammonium cation and the aromatic ring in the spacer was determined by the UV-Vis spectrum analysis, which, as well as the general electrostatic attraction and hydrophobic force, contributes to the stability of the multi-lamellar structure. The concentrations of the surface-active ions were measured for understanding the mechanism of vesicle transformation. The results show that isoelectric mixing of the two components benefits the growth of vesicles both in size and wall thickness.

  17. Solvent-Free Selective Oxidation of Toluene with O2 Catalyzed by Metal Cation Modified LDHs and Mixed Oxides

    Directory of Open Access Journals (Sweden)

    Xiaoli Wang


    Full Text Available A series of metal cation modified layered-double hydroxides (LDHs and mixed oxides were prepared and used to be the selective oxidation of toluene with O2. The results revealed that the modified LDHs exhibited much higher catalytic performance than their parent LDH and the modified mixed oxides. Moreover, the metal cations were also found to play important roles in the catalytic performance and stabilities of modified catalysts. Under the optimal reaction conditions, the highest toluene conversion reached 8.7% with 97.5% of the selectivity to benzyldehyde; moreover, the catalytic performance remained after nine catalytic runs. In addition, the reaction probably involved a free-radical mechanism.

  18. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis. (United States)

    Pucino, Margherita; Mougel, Victor; Schowner, Roman; Fedorov, Alexey; Buchmeiser, Michael R; Copéret, Christophe


    Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong σ-donating N-heterocyclic carbene ligands with weak σ-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(OTf)] and [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(+) ][B(Ar(F) )4 (-) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar(F) )4 =B(3,5-(CF3 )2 C6 H3 )4 ] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene.

  19. Thermal treatment effects imposed on solid DNA cationic lipid complex with hexadecyltrimethylammonium chloride, observed by variable angle spectroscopic ellipsometry

    Energy Technology Data Exchange (ETDEWEB)

    Nizioł, Jacek, E-mail: [Faculty of Physics and Applied Computer Science, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Kraków (Poland)


    DNA cationic lipid complexes are materials of properties required for applications in organic electronics and optoelectronics. Often, their thermal stability demonstrated by thermogravimetry is cited in the literature as important issue. However, little is known about processes occurring in heated solid DNA cationic lipid complexes. In frame of this work, thin films of Deoxyribonucleic acid-hexadecyltrimethylammonium chloride (DNA-CTMA) were deposited on silicon wafers. Samples were thermally annealed, and simultaneously, their optical functions were measured by spectroscopic ellipsometry. At lower temperatures, thermal expansion coefficient of solid DNA-CTMA was negative, but at higher temperatures positive. Thermally induced modification of absorption spectrum in UV-vis was observed. It occurred at a range of temperatures higher than this of DNA denaturation in solution. The observed phenomenon was irreversible, at least in time scale of the experiment (one day)

  20. Colorful Hydrophobic Poly(Vinyl Butyral)/Cationic Dye Fibrous Membranes via a Colored Solution Electrospinning Process (United States)

    Yan, Xu; You, Ming-Hao; Lou, Tao; Yu, Miao; Zhang, Jun-Cheng; Gong, Mao-Gang; Lv, Fu-Yan; Huang, Yuan-Yuan; Long, Yun-Ze


    Colorful nanofibrous membranes have attracted much attention for their visual varieties and various functionalities. In this article, a colored solution electrospinning process was used to fabricate colorful hydrophobic poly(vinyl butyral) (PVB)/cationic dye nanofibrous membranes (NFMs) successfully. The color and morphology of these as-spun nanofibrous membranes have been analyzed by colorimetry, spectroscopy, and scanning electron microscopy (SEM). It is shown that the as-spun colorful PVB-based membranes exhibit excellent level-dyeing property and color stability. Furthermore, the doping of cationic dye and the increase of dye concentration can decrease the diameter of the as-spun colored fibers, which results in better level-dyeing property and higher water contact angle more than 140°. The stained PVB fibrous membranes with excellent level-dyeing property and hydrophobicity are promising in some applications such as textiles, wallpapers, and anticorrosive coating/painting.

  1. Financial Intermediation, Monetary Uncertainty, and Bank Interest Margins Financial Intermediation, Monetary Uncertainty, and Bank Interest Margins

    Directory of Open Access Journals (Sweden)

    Leonardo Hernández


    Full Text Available Financial Intermediation, Monetary Uncertainty, and Bank Interest Margins This paper studies a simple model of financial intermediation in order to understand how the lending-borrowing spread or interest margin charged by financial intermediaries is determined in equilibrium in a monetary economy. The main conclusion of the paper concerns the effect on the spread of changes in the distribution of monetary innovations. Thus, changes in the monetary-policy-rule followed by the Central Bank which alter the volatility of inflation will have important effects on the interest margin and also on the amount of credit available to investors. A crosssection empirical analysis strongly supports our hypothesis:

  2. Reaction Intermediates in Aromatic Fuel Combustion. (United States)


    immediate appearance of the 254 nm emission with no delay at 1700 K, at which the dissociation of C6H 6 is slow. Additionally, the concentration of...been studied from 1600 to 2300 K in a shock tube using a stabilized CW CO laser to monitor CO production. The result of the kinetic modeling of the CO...time CO * concentration is measured by resonance absorption using a frequency-stabilized CV CO laser . Kinetic modeling of our CO * profiles as well as

  3. Fission in intermediate energy heavy ion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wilhelmy, J.B.; Begemann-Blaich, M.; Blaich, T.; Boissevain, J.; Fowler, M.M.; Gavron, A.; Jacak, B.V.; Lysaght, P.S. (Los Alamos National Lab., NM (USA)); Britt, H.C.; Fields, D.J.; Hansen, L.F.; Lanier, R.G.; Massoletti, D.J.; Namboodiri, M.M.; Remington, B.A.; Sangster, T.C.; Struble, G.L.; Webb, M.L. (Lawrence Livermore National Lab., CA (USA)); Chan, Y.D.; Dacai, A.; Harmon, A.; Leyba, J.; Pouliot, J.; Stokstad, R.G. (Lawrence Berkeley Lab., CA (USA)); Hansen, O.; Levine, M.J.; Thorn, C.E.; Trautmann, W. (Brookhaven National Lab., Upton, NY (USA)); Dichter, B.; Kaufman, S.; Videbaek, F. (Argonne National Lab. (USA)); Fraenkel, Z.; Mamane, G. (Weizmann Inst. of Science, Rehovoth (Israel)); Cebra, D.; Westfall, G.D. (Michigan State Univ., East Lansing (USA))


    A systematic study of reaction mechanisms at intermediate energies (50-100 MeV/A) has been performed at the Lawrence Berkeley Laboratory's BeValac using medium weight projectiles on medium and heavy element targets. A gas and plastic phoswich detector system was employed which gave large geometric coverage and a wide dynamic response. The particles identified with the gas detectors could be characterized into three components - intermediate mass fragments (IMF), fission fragments (FF) and heavy residues (HR). Major observed features are: The reaction yields are similar in the 50 to 100 MeV/A range, central collisions have high multiplicty of IMF's with broad angular correlations consistent with a large participant region, effects of final state Coulomb interactions are observed and give information on the size and temporal behavior of the source, true fission yields are dependent on target fissility and correlated with relatively peripheral collisions. Analysis of fission and evaporation yields implies limiting conditions for which fission decay remains a viable deexcitation channel. (orig.).

  4. Intermediate energy neutron beams from the MURR. (United States)

    Brugger, R M; Herleth, W H


    Several reactors in the United States are potential candidates to deliver beams of intermediate energy neutrons for NCT. At this time, moderators, as compared to filters, appear to be the more effective means of tailoring the flux of these reactors. The objective is to sufficiently reduce the flux of fast neutrons while producing enough intermediate energy neutrons for treatments. At the University of Missouri Research Reactor (MURR), the code MCNP has recently been used to calculate doses in a phantom. First, "ideal" beams of 1, 35, and 1000 eV neutrons were analyzed to determine doses and advantage depths in the phantom. Second, a high quality beam that had been designed to fit in the thermal column of the MURR, was reanalyzed. MCNP calculations of the dose in phantom in this beam confirmed previous calculations and showed that this beam would be a nearly ideal one with neutrons of the desired energy and also a high neutron current. However, installation of this beam will require a significant modification of the thermal column of the MURR. Therefore, a second beam that is less difficult to build and install, but of lower neutron current, has been designed to fit in MURR port F. This beam is designed using inexpensive A1, S, and Pb. The doses calculated in the phantom placed in this beam show that it will be satisfactory for sample tests, animal tests, and possible initial patient trials. Producing this beam will require only modest modifications of the existing tube.

  5. A new vaginal delivery system of amphotericin B: a dispersion of cationic liposomes in a thermosensitive gel. (United States)

    Kang, June-Woo; Davaa, Enkhzaya; Kim, Ye-Tae; Park, Jeong-Sook


    Amphotericin B (AmB) is used in the treatment of fungal infections; however, its clinical use is limited by its toxic side effects. In this study, AmB-loaded cationic liposome gels were formulated with 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE), 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP), and cholesterol (CH) at a molar ratio of DOPE:DOTAP:CH = 4:5:1 in thermosensitive gel composed of poloxamer 407 (P407) and poloxamer 188 (P188). To enhance the solubility of AmB, 6 mol% of distearoyl phosphatidyl ethanolamine-polyethylene glycol was added prior to encapsulation of the drug into liposomes. Scanning electron microscopy was used to observe the AmB encapsulated cationic liposome gels. In vitro release, stability and cytotoxicity of AmB in cationic liposome gels were evaluated. The particle size and zeta potential of AmB-loaded liposomes were in the range of 400-500 nm and 40-60 mV, respectively. The thermosensitive gel at the ratio of P407:P188 = 15:15 (w/w) gelled at 37 degrees C, approximating body temperature. Encapsulation efficiency of AmB was approximately 50-60%, which was influenced by the ratio of AmB to lipid. Moreover, AmB-loaded cationic liposome gels were more stable and less toxic than free AmB. From these results, cationic liposome gel formulations may be useful for vaginal delivery of AmB.

  6. Xe-bearing hydrocarbon ions: Observation of Xe.acetylene+rad and Xe.benzene+rad radical cations and calculations of their ground state structures (United States)

    Cui, Zhong-hua; Attah, Isaac K.; Platt, Sean P.; Aziz, Saadullah G.; Kertesz, Miklos; El-Shall, M. S.


    This work reports evidence for novel types of Xe-bearing hydrocarbon radical cations. The Xe.acetylene+rad radical cation adduct is observed at nearly room temperature using the mass-selected drift cell technique. The irreversible addition of the Xe atom and the lack of back dissociation to HCCH+rad + Xe is consistent with the calculated binding energy of 0.85 eV to be contrasted with the metastable nature of the neutral Xe.acetylene adduct. The observed Xe.benzene+rad radical cation appears to be a weakly bound complex stabilized mainly by ion-induced dipole interaction consistent with a calculated binding energy in the range of 0.14-0.17 eV.

  7. Thermodynamic and Kinetic Aspects Involved in the Development of Nanocarriers and Drug Delivery Systems Based on Cationic Biopolymers. (United States)

    Bianco, Ismael D; Alasino, Roxana V; Leonhard, Victoria; Beltramo, Dante M


    During the last years we have seen an increasing number of reports describing new properties and potential applications of cationic polymers and derived nanostructures. This review gives a summary of their applications in drug delivery, the preparation methods for nano and microstructures and will attempt to give a glimpse on how their structure, chemical composition and properties may be affected or modulated as to make them suitable for an intended application as drug delivery nanocarriers. The compositional complexity with the existence of several reacting groups makes cationic nanostructures critically sensitive to the contribution of thermodynamic and kinetic parameters in the determination of the type and stability of a particular structure and its ability to respond to changes in environmental conditions in the right time frame. Curiously, and contrarily to what could be expected, despite the fact that cationic polymers can form strong electrostatic interactions the contribution of the entropic component has been often found to be very important for their association with negatively charged supramolecular structures. Some general considerations indicate that when considering a complex multimolecular system like a nanocarrier containing an active ingredient it is frequently possible to find conditions under which enthalpic and entropic contributions are compensated leading to stable structures with a marginal thermodynamic stability (free energy change close to zero) which make them able to respond relatively fast to changes in the environmental conditions and therefore suitable for the design of smart drug delivery systems. Like with other nanocarriers, it should always be kept in mind that the properties of cationic nanocarriers will depend not only on their chemical composition but also on the properties of the structures formed by them.

  8. Protonation of a hydroxide anion bridging two divalent magnesium cations in water probed by first-principles metadynamics simulation. (United States)

    Park, Jung Mee; Boero, Mauro


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

  9. The Stabilizing Effects in Gold Carbene Complexes. (United States)

    Nunes Dos Santos Comprido, Laura; Klein, Johannes E M N; Knizia, Gerald; Kästner, Johannes; Hashmi, A Stephen K


    Bonding and stabilizing effects in gold carbene complexes are investigated by using Kohn-Sham density functional theory (DFT) and the intrinsic bond orbital (IBO) approach. The π-stabilizing effects of organic substituents at the carbene carbon atom coordinated to the gold atom are evaluated for a series of recently isolated and characterized complexes, as well as intermediates of prototypical 1,6-enyne cyclization reactions. The results indicate that these effects are of particular importance for gold complexes especially because of the low π-backbonding contribution from the gold atom.

  10. Phase stability of nickel and zirconium stannides (United States)

    Berche, A.; Tédenac, J. C.; Jund, P.


    Ni-Sn-Zr alloys have many interests in different fields of application going from nuclear material applications to functional materials (such as thermoelectrics). This wide application range requires a good knowledge of the stability of the phases. In the present study, first principles calculations are used to determine the enthalpies of formation of intermediate phases and of the structural defects in some structures. Based on these data and on the literature, the stability of the phases is discussed at low and high temperatures. Finally, for the first time the complete ternary system is described in the whole temperature range.

  11. Hypomorphic variants of cationic amino acid transporter 3 in males with autism spectrum disorders. (United States)

    Nava, Caroline; Rupp, Johanna; Boissel, Jean-Paul; Mignot, Cyril; Rastetter, Agnès; Amiet, Claire; Jacquette, Aurélia; Dupuits, Céline; Bouteiller, Delphine; Keren, Boris; Ruberg, Merle; Faudet, Anne; Doummar, Diane; Philippe, Anne; Périsse, Didier; Laurent, Claudine; Lebrun, Nicolas; Guillemot, Vincent; Chelly, Jamel; Cohen, David; Héron, Delphine; Brice, Alexis; Closs, Ellen I; Depienne, Christel


    Cationic amino acid transporters (CATs) mediate the entry of L-type cationic amino acids (arginine, ornithine and lysine) into the cells including neurons. CAT-3, encoded by the SLC7A3 gene on chromosome X, is one of the three CATs present in the human genome, with selective expression in brain. SLC7A3 is highly intolerant to variation in humans, as attested by the low frequency of deleterious variants in available databases, but the impact on variants in this gene in humans remains undefined. In this study, we identified a missense variant in SLC7A3, encoding the CAT-3 cationic amino acid transporter, on chromosome X by exome sequencing in two brothers with autism spectrum disorder (ASD). We then sequenced the SLC7A3 coding sequence in 148 male patients with ASD and identified three additional rare missense variants in unrelated patients. Functional analyses of the mutant transporters showed that two of the four identified variants cause severe or moderate loss of CAT-3 function due to altered protein stability or abnormal trafficking to the plasma membrane. The patient with the most deleterious SLC7A3 variant had high-functioning autism and epilepsy, and also carries a de novo 16p11.2 duplication possibly contributing to his phenotype. This study shows that rare hypomorphic variants of SLC7A3 exist in male individuals and suggest that SLC7A3 variants possibly contribute to the etiology of ASD in male subjects in association with other genetic factors.

  12. Alkali Cation Chelation in Cold β-O-4 Tetralignol Complexes (United States)

    DeBlase, Andrew F.; Dziekonski, Eric T.; Hopkins, John R.; Burke, Nicole L.; Kenttamaa, Hilkka I.; McLuckey, Scott A.; Zwier, Timothy S.


    Lignins are the second most abundant naturally occurring polymer class, contributing to about 30% of the organic carbon in the biosphere. Their primary function is to provide the structural integrity of plant cell walls and have recently come under consideration as a potential source of biofuels because they have an energy content similar to coal. Herein, we employ cold ion spectroscopy (UV action and IR-UV double resonance) to unravel the spectroscopic signatures of G-type alkali metal cationized (X = Li+, Na+, K+) lignin tetramers connected by β-O-4 linkages. The conformation-specific spectroscopy reveals a variety of conformers, each containing distinct infrared spectra in the OH stretching region building on recent studies on the neutral and alkali metal cationized β-O-4 dimers. Based on comparisons of our infrared spectra to density functional theory [M05-2X/6-31+G*] harmonic level calculations for structures derived from a Monte Carlo conformational search, the alkali metal ion is discovered to engage in M+-OH-O interactions as important motifs that determine the secondary structures of these complexes. This interaction disappears in the major conformer of the K+ adduct, suggesting a reemergence of a neutral dimer segment as the metal binding energy decreases. Chelation of the metal cation by oxygen lone pair(s) of nearby oxygens in the β-O-4 linkage is observed to be the predominant driving force for 3D structure around the charge site, relegating OH-O H-bonds as secondary stabilizing elements.

  13. Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products (United States)

    Fang, Yi; Liu, Fang; Barber, Victoria P.; Klippenstein, Stephen J.; McCoy, Anne B.; Lester, Marsha I.


    In the atmosphere, a dominant loss process for carbonyl oxide intermediates produced from alkene ozonolysis is also an important source of hydroxyl radicals. The rate of appearance of OH radicals is revealed through direct time-domain measurements following vibrational activation of prototypical methyl-substituted Criegee intermediates under collision-free conditions. Complementary theoretical calculations predict the unimolecular decay rate for the Criegee intermediates in the vicinity of the barrier for 1,4 hydrogen transfer that leads to OH products. Both experiment and theory yield unimolecular decay rates of ca. 108 and 107 s-1 for syn-CH3CHOO and (CH3)2COO, respectively, at energies near the barrier. Tunneling through the barrier, computed from high level electronic structure theory and experimentally validated, makes a significant contribution to the decay rate. Extension to thermally averaged unimolecular decay of stabilized Criegee intermediates under atmospheric conditions yields rates that are six orders of magnitude slower than those evaluated directly in the barrier region.

  14. Morphology Evolution of High Efficiency Perovskite Solar Cells via Vapor Induced Intermediate Phases. (United States)

    Zuo, Lijian; Dong, Shiqi; De Marco, Nicholas; Hsieh, Yao-Tsung; Bae, Sang-Hoon; Sun, Pengyu; Yang, Yang


    Morphology is critical component to achieve high device performance hybrid perovskite solar cells. Here, we develop a vapor induced intermediate phase (VIP) strategy to manipulate the morphology of perovskite films. By exposing the perovskite precursor films to different saturated solvent vapor atmospheres, e.g., dimethylformamide and dimethylsufoxide, dramatic film morphological evolution occurs, associated with the formation of different intermediate phases. We observe that the crystallization kinetics is significantly altered due to the formation of these intermediate phases, yielding highly crystalline perovskite films with less defect states and high carrier lifetimes. The perovskite solar cells with the reconstructed films exhibits the highest power conversion efficiency (PCE) up to 19.2% under 1 sun AM 1.5G irradiance, which is among the highest planar heterojunction perovskite solar cells. Also, the perovskite solar cells with VIP processing shows less hysteresis behavior and a stabilized power output over 18%. Our work opens up a new direction for morphology control through intermediate phase formation, and paves the way toward further enhancing the device performances of perovskite solar cells.

  15. Fenton degradation of sulfanilamide in the presence of Al,Fe-pillared clay: Catalytic behavior and identification of the intermediates. (United States)

    Khankhasaeva, Sesegma Ts; Dambueva, Darima V; Dashinamzhilova, Elvira Ts; Gil, Antonio; Vicente, Miguel A; Timofeeva, Maria N


    Liquid phase catalytic degradation of sulfanilamide with H2O2 was carried out in the presence of Fe,Al/M-pillared clay (Fe,Al/M-MM, M=Na(+), Ca(2+) and Ba(2+)) as heterogeneous Fenton type catalyst. Fe,Al/M-MMs were prepared by swelling of layered aluminosilicate (90-95 wt.% montmorillonite) from a bed located in Mukhortala (Buryatia, Russia) in Na(+), Ca(2+) and Ba(2+) forms by means of the exchange of these cations with bulky Fe,Al-polyoxocations prepared at Al/Fe=10/1 and OH/(Al+Fe)=2.0, and then calcinated at 500°C. XRD method and chemical analysis demonstrated that the rate of crystalline swelling was dependent on the interlayer cations and decreased in the order: Fe,Al-/Na-MM>Fe,Al/Ca-MM>Fe,Al/Ba-MM. It was found that the catalytic properties of Fe,Al/M-MMs depended on the type of exchangeable cations. The effect of the H2O2/sulfanilamide molar ratio, the catalyst content, the reaction temperature and the reaction pH on the removal rate of sulfanilamide has been studied in the presence of Fe,Al/Na-MM. The catalyst can be applied for degradation of sulfanilamide with H2O2 for at least three successive cycles without loss of activity. HPLC analyses pointed out that the main degradation intermediate products were sulfanilic acid, benzenesulfonic acid, p-benzoquinone and aliphatic carboxylic acids.

  16. Stability of solid oxide fuel cell materials

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, T.R.; Pederson, L.R.; Stevenson, J.W.; Raney, P.E. [Pacific Northwest Lab., Richland, WA (United States)


    The phase stability and sintering behavior of materials used in SOFCs has been evaluated. The sintering behavior of Ca and Sr doped lanthanum. manganite (the preferred SOFC cathode material) is highly dependent on the relative proportion of A and B site cations in the material. Ca and Sr doped lanthanum chromite (the preferred interconnect material) have been shown to rapidly expand in reducing atmospheres at temperatures as low as 700{degrees}C. This expansion is due to the reduction of Cr{sup 4+} to Cr{sup 3+} in reducing environments.

  17. Enhancing Intrinsic Stability of Hybrid Perovskite Solar Cell by Strong, yet Balanced, Electronic Coupling (United States)

    El-Mellouhi, Fedwa; Bentria, El Tayeb; Rashkeev, Sergey N.; Kais, Sabre; Alharbi, Fahhad H.


    In the past few years, the meteoric development of hybrid organic–inorganic perovskite solar cells (PSC) astonished the community. The efficiency has already reached the level needed for commercialization; however, the instability hinders its deployment on the market. Here, we report a mechanism to chemically stabilize PSC absorbers. We propose to replace the widely used methylammonium cation (CH3NH3+) by alternative molecular cations allowing an enhanced electronic coupling between the cation and the PbI6 octahedra while maintaining the band gap energy within the suitable range for solar cells. The mechanism exploits establishing a balance between the electronegativity of the materials’ constituents and the resulting ionic electrostatic interactions. The calculations demonstrate the concept of enhancing the electronic coupling, and hence the stability, by exploring the stabilizing features of CH3PH3+, CH3SH2+, and SH3+ cations, among several other possible candidates. Chemical stability enhancement hence results from a strong, yet balanced, electronic coupling between the cation and the halides in the octahedron. This shall unlock the hindering instability problem for PSCs and allow them to hit the market as a serious low-cost competitor to silicon based solar cell technologies.

  18. Responsive Aqueous Foams Stabilized by Silica Nanoparticles Hydrophobized in Situ with a Conventional Surfactant. (United States)

    Zhu, Yue; Pei, Xiaomei; Jiang, Jianzhong; Cui, Zhenggang; Binks, Bernard P


    In the recent past, switchable surfactants and switchable/stimulus-responsive surface-active particles have been of great interest. Both can be transformed between surface-active and surface-inactive states via several triggers, making them recoverable and reusable afterward. However, the synthesis of these materials is complicated. In this paper we report a facile protocol to obtain responsive surface-active nanoparticles and their use in preparing responsive particle-stabilized foams. Hydrophilic silica nanoparticles are initially hydrophobized in situ with a trace amount of a conventional cationic surfactant in water, rendering them surface-active such that they stabilize aqueous foams. The latter can then be destabilized by adding equal moles of an anionic surfactant, and restabilized by adding another trace amount of the cationic surfactant followed by shaking. The stabilization-destabilization of the foams can be cycled many times at room temperature. The trigger is the stronger electrostatic interaction between the oppositely charged surfactants than that between the cationic surfactant and the negatively charged particles. The added anionic surfactant tends to form ion pairs with the cationic surfactant, leading to desorption of the latter from particle surfaces and dehydrophobization of the particles. Upon addition of another trace amount of cationic surfactant, the particles are rehydrophobized in situ and can then stabilize foams again. This principle makes it possible to obtain responsive surface-active particles using commercially available inorganic nanoparticles and conventional surfactants.

  19. Enhancing Intrinsic Stability of Hybrid Perovskite Solar Cell by Strong, yet Balanced, Electronic Coupling (United States)

    El-Mellouhi, Fedwa; Bentria, El Tayeb; Rashkeev, Sergey N.; Kais, Sabre; Alharbi, Fahhad H.


    In the past few years, the meteoric development of hybrid organic–inorganic perovskite solar cells (PSC) astonished the community. The efficiency has already reached the level needed for commercialization; however, the instability hinders its deployment on the market. Here, we report a mechanism to chemically stabilize PSC absorbers. We propose to replace the widely used methylammonium cation (CH3NH3+) by alternative molecular cations allowing an enhanced electronic coupling between the cation and the PbI6 octahedra while maintaining the band gap energy within the suitable range for solar cells. The mechanism exploits establishing a balance between the electronegativity of the materials’ constituents and the resulting ionic electrostatic interactions. The calculations demonstrate the concept of enhancing the electronic coupling, and hence the stability, by exploring the stabilizing features of CH3PH3+, CH3SH2+, and SH3+ cations, among several other possible candidates. Chemical stability enhancement hence results from a strong, yet balanced, electronic coupling between the cation and the halides in the octahedron. This shall unlock the hindering instability problem for PSCs and allow them to hit the market as a serious low-cost competitor to silicon based solar cell technologies. PMID:27457130

  20. VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes

    CERN Document Server

    Zhen, Junfeng; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M


    Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7-20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ~13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies, all species be...